In this study, a new and facile process was developed for the preparation of composite catalysts based on tungsten oxide (WO3) by batch reactor routes. The structures, morphologies, compositions, and characteristics of synthesized materials were investigated and confirmed. Using batch reactor processes, WO3 nanorods (WO3 NR), heterostructures of WS2/WO3 nanobricks (WS2/WO3 NB), and WS2/WO3 nanorods (WS2/WO3 NR) were successfully prepared. The prepared materials were then employed for hydrogen evolution reaction (HER) to investigate their catalytic performance. The results indicated that the electrocatalytic activities of WS2/WO3 NR are significantly improved compared to those of WO3 NR and WS2/WO3 NB. This improvement could be attributed to the formation of heterostructure between WS2 and WO3 elements in highly uniform materials, which could create the synergistic effect and further improve the catalytic activities of the catalyst. The data shows that the Tafel slope of WS2/WO3 NR (82.7 mV dec−1) is significantly lower than that of WO3 NR (112.5 mV dec−1) and WS2/WO3 NB (195.5 mV dec−1). Furthermore, the resistance of WS2/WO3 NR (397.7 Ω) is markedly decreased compared to those of WO3 NR (1816 Ω) and WS2/WO3 NB (3597 Ω). The results indicate that WS2/WO3 NR could be a great catalyst for electrochemical applications.