Searching for non-noble metal catalysts with high activities and low price is critical to the commercialization of methanol oxidation in the process of fuel cells.Herein,two new pseudo-isomeric Ni metal-organic frameworks (Ni-MOFs) (CTGU-17/CTGU-18) have been prepared with 1,4-naphthalenedi-carboxylate (H2NDC),4,4'-dipyridyl amine (DPA) and Ni(ClO4)2 under hydrothermal condition.Each phase contains one water molecule,but differs dramatically in its bonding to the framework,resulting in different topological networks with fourfold interpenetrating 4-connected dia net (CTGU-17) and (3,7)-connected net (CTGU-18) and diverse electrocatalytic performance for methanol oxidation reaction (MOR).Remarkably,by combining each MOF with the conductive additive,acetylene black (AB),a composite material,AB&CTGU-18(2:4) was confirmed to have an excellent performance for MOR with a high mass specific peak current of 442.3 mA·mg-1.The enhanced electrocatalytic activities and robustness might be attributed to the synergetic effect of acetylene black and the active metal centers of MOFs particles for methanol oxidation.The present work would provide a new insight for the rational design of MOFs-based composites with enhanced methanol oxidation reaction performance.