Pt/C catalysts containing four different morphologies of CeO2 as co-catalysts were synthesized in this work, and their electrocatalytic performance for hydrogen evolution reaction (HER) was investigated. As compared with the Pt/C catalyst, these four catalysts containing CeO2 all exhibited improved catalytic activity. Among them, the Pt/C catalyst containing spherical CeO2 with a diameter of 30 ~ 60 nm (Pt/C-CeO2(s2)) possesses the best catalytic activity, displaying an over-potential of 258 mV at 10 mA cm−2 and a Tafel slope of 42 mV dec−1. According to the characterization results of structure, morphology, and elemental valence state, the enhancement of catalytic activity is ascribed to the small particle size and good dispersion degree of Pt, as well as the strong interaction between the exposed (111) crystal plane of small spherical CeO2 and Pt, which leads to a significant increase in metallic Pt content. Moreover, the Pt/C-CeO2(s2) catalyst also demonstrates outstanding long-term stability besides exceptional catalytic activity. The results clearly illustrate that CeO2 with diverse shapes and sizes can remarkably influence the catalytic performance of loaded Pt particles in the HER process.