Platinum-decorated graphene aerogel microspheres were fabricated through a combined electrospraying, freeze-casting, and solvothermal process. Platinum nanoparticles with a narrow size distribution are evenly anchored on the graphene aerogel microspheres without agglomeration benefitting from the distinct center-diverging microchannel structure of the graphene aerogel microspheres, which results in the as-prepared catalysts presenting excellent electrocatalytic performance including high electrocatalytic activity and high poison tolerance toward methanol electro-oxidation, showing great potential for direct methanol fuel cell anode catalysts. In particular, the platinum-decorated graphene aerogel microspheres exhibit an extremely high mass activity of 1098.9 mA mg-1 toward methanol oxidation as well as excellent antipoisoning ability, which are dramatically enhanced compared with Pt particles dispersed on graphene oxide and commercial carbon black supports.