Although direct methanol fuel cell offers high energy use efficiency and low pollution emission, the lack of suitable electrode materials poses a great challenge to its commercial application. Herein, a facile and scalable approach is developed to fabricate a hybrid electrocatalyst consisting of strongly coupled worm‐shape Pt nanocrystals and nitrogen‐doped low‐defect graphene (N‐LDG) sheets. Interestingly, it is found that the formation of Pt nanoworms (NWs) is induced by the N atoms in the high‐quality carbon matrix, which also allows the integration of their respective structural advantages and leads to a strong synergetic coupling effect. As a result, the obtained Pt NW/N‐LDG catalyst exhibits an extremely high mass activity of 1283.1 mA mg−1 toward methanol oxidation reaction, accompanied by reliable long‐term stability and good antipoisoning ability, which are dramatically enhanced as compared with conventional Pt nanoparticle catalysts dispersed on undoped LDG, reduced graphene oxide, and commercial carbon black supports. The growth of Pt nanoworms on nitrogen‐doped low‐defect graphene is achieved by a combined CVD, heat treatment, and solvothermal method. Owing to the prominent structural features including large surface areas, well‐preserved pristine graphene structure, presence of catalytically active N atoms, and interconnected worm‐shape Pt configuration, the resulting hybrid is endowed with exceptional electrochemical properties toward methanol oxidation reaction.