The commonly used CuO/ZnO catalysts are prone to show unsatisfying performance at higher temperatures for hydrogen generation through methanol steam reforming (MSR) reaction, and thus catalyst modifications are required to enhance the performance of catalysts. In this study, CuO/ZnO was successfully loaded on a metal-organic framework material (Cu-BTC) by the impregnation method, with different masses of Cu-BTC. The catalyst ingredients and microstructure were characterized, and the catalytic performance at the temperature range from 200 to 340 °C was investigated in an MSR test system. The catalytic activity, anti-deactivation ability and stability performance of CuO/ZnO/Cu-BTCs were found to be much better than that of CuO/ZnO. The hydrogen concentration and hydrogen generation rate of CuO/ZnO/Cu-BTCs with 0.5 and 1 g Cu-BTC were increased by about 100% and 1000%, respectively, compared with the CuO/ZnO catalyst at 300 °C. Although superfluous Cu-BTC caused the evident reduction of catalytic activity at low temperatures, no obvious deactivation happened at higher temperatures. The deposition of CuO/ZnO on Cu-BTC has great potential to enhance the performance at higher temperatures for hydrogen generation through MSR reaction.