The hydrogen evolution reaction activity of carbon-supported Pt catalyst is highly dependent on Pt-C interfaces. Herein, we focus on the relationships between Pt activity and N/O-functionalized hollow carbon sphere (HCS) substrate in acidic media. The electrochemical dissolution of Pt counter electrode is performed to prepare Pt nanoparticles in low loading. The N groups are beneficial for homogeneously sized Pt nanoparticles, whereas the O groups lead to aggregated nanoparticles. Moreover, the proper electronegativity of the N groups may enable capturing of protons to create proton-rich Pt-C interfaces and transfer them onto the Pt sites. The O groups may also capture protons by hydrogen bonding, but the subsequent release of protons is more difficult due to a stronger electronegativity and result in an inferior Pt activity. Consequently, the N-doped HCS with a low Pt loading (1.7 μg cm-2 and 0.05 wt %) possesses a higher intrinsic activity compared with Pt on O-doped HCS. Moreover, it outperforms the commercial 20% Pt/C with a stable operation for 12 h. This work may provide suggestions for constructing the advantageous Pt-C interfaces by proper functional groups for high catalytic efficiencies.