Computational chemistry has helped so far not only to understand the regioselectivity of a wide variety of chemical functionalizations on C₆₀ and endohedral metallofullerenes (EMFs), but also to disclose in many cases their reaction mechanisms. In this communication we will show the recent progress on our group related to different topics, as (1) the prediction of halogenation and hydrogenation of EMFs confirmed by experiments; and (2) the analysis of stereoselective reactions on C₆₀ hexaadducts, as well as other related systems.