For heterogeneous catalysis reaction, the facet effect plays an important role in affecting the activity of the catalyst. In this paper, we prepared Pd catalysts exposed to (111) and (100) crystal planes by controlling the type of end capping agent and the structure of the catalysts were characterized using techniques such as TEM, XRD, XPS. The eosin Y (EY) sensitized Pd catalysts were used to catalytic hydrogen production from formaldehyde driven by visible light under alkaline conditions. The experimental results show that the Pd(100)/RGO catalyst exhibits highest catalytic performance, the hydrogen evolution rate was 86.85μmol/h. This can be attributed to the strong interaction between the Pd(100) facet and graphite oxide, which is conducive to improving the transfer rate on the catalyst surface. In addition, the dissociation energy barrier of oxygen molecules on the surface of the Pd(100) catalyst is an important reason for the high activity of the catalyst. Our results give a new viewpoint to the development of high efficiency catalysts for hydrogen evolution from formaldehyde.