Haven't been to Africa yet, but have done much research for a (hopefully soon) jaunt through Africa.
As #4 alluded to, the CFA franc (used in all of W. Africa, except Mauritania, Guinea, Sierra Leone, Liberia, Ghana, & Nigeria) was fixed 100:1 to the french franc and thus now fixed to the Euro (655:1)...so the Euro is supreme there. In North Africa, Euros are more-readily exchanged, due to the volume of European tourists as well as expats in Europe sending their money home. Morocco & Egypt will take both as readily.
Everywhere else in sub-Saharan Africa, the dollar is king. As mentioned, many borders will accept visa fees only in dollars. Also, most banks are reluctant to give dollars. In a few random locations, though, getting dollars isn't terribly hard. I can't recall the exact countries, but I remember reading that in some places in West Africa (I might guess in parts of Nigeria) ATMs dispense dollars. I would image that in Zimbabwe, which has recently switched to the dollar as the de facto currency, dollars may be found at banks. Also, many hotels (even backpacker hostels) give their rates in dollars, especially in tourist-prone places.
If travelling in southern African countries (I know at least Namibia, Botswana, Zimbabwe, and likely Lesotho & Swaziland), the South African rand is easy to exchange and/or use (the Namibian currency is fixed 1:1). The pound sterling is familiar to many Comonwealth countries, but still not as accepted as USD. Other major currencies like Euros (outside WA), Aussie dollars, yen, & Canadian dollars can only be traded at some of the largest African banks.
Be careful to use all your local currency before crossing borders (keep just a little if taking a bus across a border as you will want drinks/food on what can be very long rides). This is especially true in West Africa, where changing CFA francs in countries like Ghana or Nigeria (and vice versa) is next to impossible...even in towns near the border! Also important to note is that the west African CFA franc (used from Senegal east to Benin/Niger) and the central African CFA franc (Chad south to R. Congo/CAR) are NOT interchangeable even though they have the same value and name!! You can tell as the banknotes have different designs.
When exchanging USD/Euros, the larger notes will fetch better exchange rates, while a small amount of small notes will be useful in places where prices are small and in USD (some tourist attractions, border crossings, and countries like Zimbabwe where dollars are accepted by everyone). Because of counterfeiting concerns, banks will not accept older or poor condition notes and in turn vendors/exchangers/etc will not take them. Try to bring only 2003 or newer dollars which are in decent condition (especially the newer $5, $10, $20, & $50 notes with color). Not sure whether there is such a concern about Euro banknotes.
As far as how to get money, your best bet is probably to use ATMs. Today every city and town has at least one ATM to use. If using a debit/bank card, take note of the international networks it uses (there are images on the back) such as Plus, Interlink, Star. Many major banks' ATMs will be connected to such international networks to allow you to withdraw money straight from your checking account. To be on the safe side, just stop at your bank and inform them of your African travels so your card isn't flagged (or worse cancelled) because of fraud concerns (frequent withdrawals from your account from Africa are bound to raise flags). Keep in mind that most ATMs have a withdrawal limit of US$100-200 (although you can visit multiple ATMs for more $$). If your debit/bank card is affiliated with Visa or Mastercard, you can only worry about finding ATMs with the Visa or Mastercard logo. It is helpful to have BOTH a Visa and a Mastercard-affiliated debit/bank/credit card as you will find many smaller cities where only one of those ATM can be found (or at least is easy to find). Be sure to use in-bank or indoors ATMs (such as in non-crowded malls/stores) and certainly NOT ones outdoors along streets to minimize your chance of being robbed. Another thing to note is that ATMs have proliferated in the last decade, so if others who comment that there aren't that many ATMs and haven't been to Africa in the last five years, they could be quite wrong.
Worldwide Visa ATM locator
Worldwide Mastercard ATM locator
In addition to those, the
Bradt line of travel guides include ATMs for all cities/towns/villages. If you will only (or primarily) be visiting a couple of countries, the Bradt guides as good as you can get and the mentioning of ATMs only makes them better. I believe South Africa, Egypt, Libya, Chad, Mauritania, CAR, Somalia, Namibia, Lesotho, & Swaziland are the only African countries for which they do not have a guide book.
A credit card is great for an emergency and you should carry at least one, but all the interest that adds up can be a boon. Cash advances using them will also incur lots of fees from both Visa/Mastercard and the bank you are getting an advance from. A good thing for safety would be to scan or photograph your card and email it to yourself, so you can cancel it if lost.
Travelers' cheques are easy to cash in most cities, but difficult to cash in most smaller cities and towns. Many banks will reject them outright. Unlike most Western countries, they receive a POORER exchange rate than cash. However, they are replaceable if stolen and a good emergency stash in addition to credit cards. Also, if you live in a country where it's hard to get ahold of USD, you may be better off bringing Aus$/Can$/Euro/etc travelers' cheques to exchange than face the fees associated with exchanging your currency into USD then into local currencies. Same as with credit cards, scan/photograph and email to self in case you lose the numbers (cash them in order to help you know which you've spent and which may have been stolen).
So to sum things up, plan on using your debit/bank card for the majority of cash and USD/Euros for a minority and keep a credit card or travelers' cheques for emergencies. I'll let others chime in on how to keep your money safe.
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