Herein, we reported a kind of single Pt site (Pt-SA) stabilized on an MXene support (Pt-SA/MXene) via the formation of Pt–O and Pt–Ti bonds to effectively catalyze the hydrogen evolution reaction (HER). Due to the local electric field polarization derived from its unique asymmetric coordination, Pt-SA/MXene displays remarkably higher catalytic HER activity in an alkaline electrolyte. In detail, the Pt-SA/MXene electrocatalyst only needs a low overpotential of 33 mV to reach a current density of 10 mA cm⁻² and maintains the performance over 27 h. Besides, Pt-SA/MXene also has a competitive mass activity, 23.5 A mg_Pt ⁻¹, at an overpotential of 100 mV, which is 29.4 times greater than that of the commercial Pt/C counterpart. Density functional theory (DFT) calculations revealed that the polarized electric field could efficiently tailor the electronic structure of Pt-SA/MXene and reduce the energy barrier of adsorption/desorption of the H* intermediate step, further improving its HER catalytic activity.