In this paper, thick, metallic bright electrodeposited tungsten rich Ni–W–P alloy coatings with two different compositions Ni-36.3wt%W-3.3wt%P (designated as Ni–W–LP) and Ni-19.5wt%W-7.7wt%P (designated as Ni–W–HP) were chosen for comparison of heat-treatment dependent evolution of crystal structure, grain growth, nanohardness and tribological properties with respect to Ni-50.7wt%W coating. The systematic temperature dependent evolution of crystal structure and phases from as-deposited amorphous alloys were mapped using in-situ high temperature GIXRD investigation and peak-broadening analysis. Subsequent variation of nanohardness/microhardess was measured. Detailed tribological investigation of both as-deposited and heat-treated coatings was done by ball-on-plate dry sliding experiment and the observed coefficient of friction and wear data were correlated with measured nanohardness, H/E and H3/E2 ratio and a wear mechanism was proposed based on detailed FESEM investigation of wear scars.