Sodium borohydride reduced electroless Ni–B coatings possess high hardness, wear resistance, and low coefficient of friction. They are found to be suitable candidates for wear reduction of mechanical components. In a quest to achieve enhanced tribological behavior and high thermal stability, the present work reports the inclusion of W to Ni–B coatings. Electroless method is employed for Ni–B–W coating deposition on AISI 1040 steel specimens. Post deposition, the coatings are heat treated at 350 ℃, 400 ℃, and 450 ℃. Deposit characterization is carried out using energy-dispersive X-ray analysis, X-ray diffraction, and scanning electron microscopy. Inclusion of W leads to an increase in microhardness and thermal stability of Ni–B coatings. The tribological behavior of as-deposited and heat-treated Ni–B–W coatings are investigated at room and elevated temperatures (100 ℃, 300 ℃, and 500 ℃). Heat-treated coatings show lower wear rate at room temperature compared to as-deposited ones but the coefficient of friction increases. Tribological test results at elevated temperatures suggest an improvement in the wear resistance and coefficient of friction at 300 ℃ and 500 ℃ in comparison with 100 ℃. Phase transformation study post wear test indicate microstructural changes in the coating due to the in situ heat treatment at high temperature. The tribological behavior of the coatings at 100 ℃ and 300 ℃ is mainly governed by the loose wear debris and formation of debris patches, respectively. Whereas at 500 ℃, formation of protective tribo-oxide patches is also observed.