As a typical two-dimensional (2D) MXene, Ti3C2O2 has been considered as a potential material for high-performance hydrogen evolution reaction (HER) catalyst, due to its anticorrosion and hydrophilic surface. However, it is still a challenge to improve the Ti3C2O2 surficial HER catalytic activity. In this work, we investigated the HER activity of Ti3C2O2 after the surface was doped with S, Se, and Te by the first principles method. The results indicated that the HER activity of Ti3C2O2 is improved after being doped with S, Se, Te because the Gibbs free energy of hydrogen adsorption (ΔGH) is increased from −2.19 eV to 0.08 eV. Furthermore, we also found that the ΔGH of Ti3C2O2 increased from 0.182 eV to 0.08 eV with the doping concentration varied from 5.5% to 16.7%. The HER catalytic activity improvement of Ti3C2O2 is attributed to the local crystal structure distortion in catalytic active sites and Fermi level shift leads to the p-d orbital hybridization. Our results pave a new avenue for preparing a low-cost and high performance HER catalyst.