Seawater electrolysis is a potentially cost‐effective approach to green hydrogen production, but it currently faces substantial challenges for its high energy consumption and the interference of chlorine evolution reaction (ClER). Replacing the energy‐demanding oxygen evolution reaction (OER) with the methanol oxidation reaction (MOR) represents a promising alternative, as the MOR occurs at a significantly low anodic potential, which cannot only reduces the voltage needed for electrolysis but also completely circumvents the ClER. To this end, developing high‐performance MOR catalysts is a key. Herein, we report a novel quaternary Pt1.8Pd0.2CuGa/C intermetallic nanoparticles (i‐NPs) catalyst, which shows a high mass activity (11.13 A mgPGM−1), a large specific activity (18.13 mA cmPGM−2), and outstanding stability toward alkaline MOR. Advanced in‐situ surface‐enhanced Raman spectroscopy (SERS), online differential mass spectrometry (DEMS) and density functional theory (DFT) calculations reveal that the introduction of atomically distributed Pd in Pt2CuGa intermetallic markedly promotes the oxidation of key reaction intermediates by enriching electron concentration around Pt sites, resulting in weak adsorption of carbon‐containing intermediates and favorable adsorption of the synergistic OH− groups near Pd sites. Using Pt1.8Pd0.2CuGa/C i‐NPs as anodic catalysts, we demonstrate MOR‐assisted seawater electrolysis that continuously operates under 1.23 V for 240 h in simulated seawater and 120 h in natural seawater without notable degradation, showing great potential for energy‐saving and cost‐competitive hydrogen production from seawater.This article is protected by copyright. All rights reserved