Janus materials, with unique physical and chemical properties, show promise in turning solar energy into clean hydrogen through photocatalytic water splitting. Herein, utilizing first-principles calculations, we have confirmed the stabilities of newly discovered two-dimensional XY materials (X/Y=P, As, Sb, Bi, X≠Y), unveiling their promising capabilities in photocatalytic water splitting. These Janus structures exhibit broad bandgaps, paired with remarkable electron carrier mobilities. Their out-of-plane piezoelectric coefficients (d31) varying from 0.10 pm/V to 0.31 pm/V, surpass those of many typical two-dimensional materials, highlighting their considerable potential in energy conversion applications. These materials stand out in water splitting due to their favorable band edges and electrostatic potential gradients, achieving solar-to-hydrogen (STH) efficiencies above 20 % and visible light absorption efficiencies over 10 %. Remarkably, Janus PBi showcases STH and visible light absorption efficiencies up to 29.01 % and 19.33 %, respectively. By using biaxial strain, Janus PAs and PSb can reach a peak STH efficiency of over 30 % and a top visible light absorption efficiency above 20 %. Janus AsSb (PBi) exhibits exceptionally high photocatalytic activity for the oxygen (hydrogen) evolution reaction. These attributes suggest that these Janus XY materials are promising contenders as photocatalytic catalysts for water-splitting applications.