Mg/Fe layered double hydroxides (LDHs) modified with Cu and W support were synthesized by a one-pot coprecipitation method. The resulting samples were extensively characterized using TGA, XRD, UV, FTIR, SEM, EDX, TEM, and N2 adsorption-desorption techniques. Finally, the calcined LDHs were evaluated for photocatalytic hydrogen production from triammonium phosphate-water solution under solar light irradiation. The XRD results demonstrated that all as prepared LDH samples had characteristic hydrotalcite phase and validated the formation of a well-crystallized layered structure. After calcination, the LDHs exhibited a sintered, broken-down morphology with 8–40 nm particles. The adsorption-desorption isotherms of the calcined LDHs were categorized as type IV with H3–H2 hysteresis, suggesting condensation capillarity and monolayer formation. The band gap values were 1.5 eV for Mg/Fe, 2.4 eV for Cu/Mg/Fe, and 2.8 eV for W/Mg/Fe calcined LDHs. In hydrogen evolution experiments, the Mg/Fe catalyst showed the highest volume of 45.3 ml, followed by Cu/Mg/Fe (43.7 ml) and W/Mg/Fe (40.1 ml). This was attributed to the higher BET surface area of 172 m2/g for Mg/Fe compared to 38 m2/g for W/Mg/Fe and 14 m2/g for Cu/Mg/Fe, enabling better distribution of active sites.