The MacMillan Dictonary examples provided by Chris are, of course, correct but I my understanding is that "to complain of" is usually complaining about something that concerns you more directly, personally and intimately.
As Chris and Jane have both said, one can complain of an ailment (such as arthritis or gout). Or, as in the case of the MacMillan example, people might complain of being robbed. If you complain about something, that something might be a bit more detached from you and not affect you quite so directly or personally. Here's a couple of examples:
People in Seoul often complain about the air pollution but don't feel empowered to do anything about it. Within a few days of arriving in Seoul, the tourist complained of having difficulty breathing caused by the air pollution in the city.
Visitors to (pick your favorite dangerous city) complain about the need to be on the lookout for pickpockets and thieves. My friends complained of having been robbed at gunpoint in broad daylight.
Hope that helps.