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The present work involves synthesis, characterisation and evaluation of hardness and sliding wear resistance of electrodeposited nanocrystalline Ni–Fe–W alloys. The crystallite size reduced with an increase in current density owing to an increase in the amount of alloying elements (Fe and W). Ni–Fe–W alloy with 23 at.-%Fe and 1·3 at.-%W plated at 0·1 A cm−2 exhibited the maximum hardness of 563 HV. The alloys exhibited a direct Hall–Petch relation above a crystallite size of 12 nm and an inverse Hall–Petch relation below 12 nm. The wear resistance of the alloys increased with a reduction in the crystallite size in the direct Hall–Petch region and decreased in the inverse Hall–Petch region. Ni–Fe–W coatings with 23 at.-%Fe and 1·3 at.-%W plated at 0·1 A cm−2 exhibited superior wear resistance.