From Mexico City:

Highway:
Take the high way toward Toluca city in the State of Mexico, the toll free high way starts on Cuajimalpa, and the toll highway exit is through Sta. Fe, it is a two lane road on each direction. The toll is $80.00 per car. Both roads are quite good.
As soon as you get to Toluca you have to ride on the Paseo Tollocan for a while, there are 3 options from this point to Valle de Bravo:
76 km on highway15 and the detour to Amanalco (in pretty bad conditions)
75 km on highway 130 to Temascaltepec and detour to Valle de Bravo. (the shortest but with lots of curves)
88 km on highway15 to Villa Victoria and the detour to Donato Guerra and at last Valle de Bravo (the longest but with more straight sections)
From Toluca on the 3 highways are toll free.