I presume you are asking connected to the airports in Italy? The answer is yes, you can. it is more complicated then it seems as first however. The travel books always advise you to book from outside Italy as part of a package, before you get here, as that seems to be the cheapest way to do it.

At all the airports there are the normal care hire companies that you find everywhere, although their English may not be so good, but they should be able to manage the basics. Im not sure where you are from though.

As concerns the licence if you are from Europe, UK or the United states(With a licence card including photo) that should suffice.
However if you are from somewhere else, they may need a translation of your licence to an EU one, and the Automobile Association offer this service, which lasts for a year.
Apply before you come, in your own city. Beware of the driving, it takes some getting used to.