The invention discloses a compounding method of palladium and a graphene structural carbon material (selected from one of graphene, carbon nanotube or fullerene), and helps to prepare a palladium/graphene structural carbon material combined electrode catalyst. The compounding method comprises the following steps: putting a graphene structural carbon material in 1-methyl-2-pyrrolidone and performing ultrasonic dispersion; respectively adding glycol and a palladium nitrate solution and mixing uniformly, then transferring the mixed system in a hydro-thermal kettle for a reaction, after the reaction is finished, centrifugally separating to obtain a solid product, performing washing and drying to obtain the palladium/graphene structural carbon material combined electrode catalyst. According to the compounding method, the graphene structural carbon material is taken as a substrate; and by employing the hydro-thermal synthetic method, the prepared palladium/graphene structural carbon material combined electrode catalyst has better application prospect and economical benefit in the field of direct methanol fuel cells.