AbstractWith the rapid economic development and urgent environmental demands, the direct methanol fuel cell (DMFC) as one of environmental‐friendly energy‐conversion systems has attracted wide attention in the world, while the insufficient activity and low structural stability of the anode Pt/carbon catalyst largely deteriorate its overall performance. Herein, we report a facile and cost‐effective bottom‐up method to the fabrication of rhodium nanocrystals supported by three‐dimensional (3D) porous hybrid networks constructed from low‐defect carbon nanotubes and reduced graphene oxide (Rh/LCNT‐RGO) as Pt‐alternative electrocatalysts for DMFC. Such a structural design gives the resultant Rh/LCNT‐RGO hybrid a series of fantastic architectural advantages, such as the large specific surface area of 3D interconnected graphene configuration, high electrical conductivity of low‐defect carbon nanotubes, and abundant catalytically active sites of well‐dispersive Rh nanocrystals. As a consequence, the Rh/LCNT‐RGO hybrid displays unusual catalytic abilities towards the methanol electrooxidation, including a large electrochemically active surface area of 123.8 m2 g−1, a high mass activity of 1228.5 mA mg−1, strong poison tolerance, and long lifespan, far surpassing those of reference Rh/carbon black, Rh/acid‐treated CNT, and Rh/RGO catalysts.