A central challenge in large scale sustainable hydrogen production by electrolyzing water is to develop efficient and economical electocatalysts with nanostructural materials. This work herein reports the facile solvothermal synthesis of MoS2/Co3S4 hollow nanostructural co-catalyst with high activity and stability for electrochemical hydrogen evolution reaction (HER) by compositing cheap and HER-active MoS2 on Co3S4 HER catalyst. By morphology and structure modulations, this high-quality nanostructure, which is confirmed by several characterizing techniques, can be considered as excellent catalyst to split water into H2 in a wide pH range via the electric drive. Corresponding electrochemical measurement results of 55.6 mV dec−1 and 115.3 mV dec−1 Tafel slope in acid (pH = 0.3) and alkaline (pH = 14) media demonstrates our predictions. We believe that such performance improvement is mainly due to the much increased active sites for catalysis because of composition process and hollow structure. These findings open up an effective and propagable strategy for nanostructural HER catalysts synthesis.