The　electrochemical　hydrogen　evolution　reaction　(HER)　in　alkaline　medium　is　of　great　significance　for　the　conversion　of　renewable　energy　into　hydrogen　fuel.　Most　catalysts　exhibit　limited　HER　performance　in　alkaline　electrolytes　due　to　the　inefficient　dissociation　of　water　to　initiate　the　Volmer　reaction.　Herein,　we　report　the　atomically　dispersed　tungsten　(W)-optimized　MoP　nanoparticles　on　N,P-doped　graphene　oxide　(W0.25Mo0.75P/PNC)　that　possesses　high　activity　with　impressively　low　overpotentials　(eta　=　70　mV@10　mA　cm(-2),　eta　=　49　mV@10　mA　mg(cat.)(-1))　in　alkaline　medium.　The　catalyst　features　with　the　atomically　isolated　W　atoms　that　can　optimize　the　surface　electronic　structure　by　occupying　the　vacant　Mo　sites　in　the　MoP　lattice,　corroborated　by　the　X-ray　absorption　spectra,　further　leading　to　moderate　hydrogen　adsorption　energy　on　the　surface.　The　first-principles　computation　reveals　that　the　atomically　dispersed　W　atoms　effectively　reduce　the　water　dissociation　energy　and　facilitate　the　adsorption　kinetics,　leading　to　high　activity.　This　work　proposes　an　elegant　design　principle　based　on　the　pseudo-single-atom　strategy　to　facilitate　hydrogen　electrocatalysis.