Sure, it gives you a lot of freedom and flexibility to drive yourself. Especially if you are planning to go off-the-beaten-track and travel with more people, renting (or bringing) a car is a great option. Mexico Finder offers a variety of self-drive programs (including a road map). We recommend using a GPS. It will help you if you have some knowledge of Spanish. If you decide to drive yourself, we advise you to check the security situation in the region you are going to travel. Drive during the day, not at night, and if possible, use toll roads. Be aware of a huge traffic density in major cities, especially in Mexico City during rush hours, and watch out for "topes" (speed bumps), stop signs ("Alto"), and holes in the road (especially in rural areas).
Mexico has an extensive infrastructure of roads and intercity highways. Driving in Mexico is a great way to explore the country, it can be a very enjoyable and safe experience; you'll need to exercise extra care, especially in urban areas where traffic congestion is higher.