The heterogeneously structured nanomaterials usually exhibit enhanced catalytic properties in comparison with each one of the constituent materials due to the synergistic effect among their different domains. Within the last decade, the development of wet-chemistry methods leads to the blossom of research in materials with heterogeneous nanostructures, which creates great opportunities also a tremendous challenge to apply these materials for highly efficient energy conversion. We herein would systematically introduce the latest research developments in Pt-based nanomaterials with heterogeneous structures, e.g. core-shell, hollow interiors, stellated/dendritic morphologies, dimeric, or composite construction, and their potential applications as electrocatalysts toward direct methanol fuel cell reactions, including methanol oxidation reaction and oxygen reduction reaction in acidic conditions, aiming at the summarization of the fundamentals and technical approaches in synthesis, fabrication and processing of heterogeneous nanomaterials so as to provide the readers a systematic and coherent picture of the filed. This review will focus on the intrinsic relationship between the catalytic properties and the physical or/and chemical effects in the heterogeneous nanomaterials, providing for technical bases for effectively developing novel electrocatalyts with low cost, enhanced activity and high selectivity.