To ensure the green and sustainable advancement of hydrogen energy, there is a critical need for the development of a cost-effective catalyst to address the sluggish kinetics of water electrolysis under alkaline conditions. An approach to achieve this is by constructing ultrathin Pt shell-structured catalysts that offer enhanced electrocatalytic hydrogen evolution reaction performance through modulation of the inner core while minimizing costs. Herein, an ultrathin Pt shell catalyst with an inner core consisting of a PtNi face-centered cubic and hexagonal-close-packed mixed-phase interface (named PtNi-mix) is synthesized through a pre-synthesis method followed by post-acid etching process. Encouragingly, the PtNi-mix catalyst only requires 12.9 mV overpotential to achieve a current density of 10 mA·cm⁻² in 1 M KOH, which is much lower than that of the commercial 20 wt.% Pt/C catalyst (71.2 mV). Also, it possesses a high mass activity (7.2 A·mg⁻¹) at an overpotential of 70 mV, which is 9 times higher than that of the commercial 20 wt.% Pt/C catalyst. Additionally, the performance of the PtNi-mix catalyst remains almost unchanged after 10,000 cyclic voltammetry tests, indicating that the catalyst exhibits excellent stability.