The processes of the formation of the nanocomposite coating of Ni–11.5% P–5%W were studied during the heat treatment of amorphous electrodeposited layers. Using the method of differential scanning calorimetry, the temperature of the onset of crystallization of the nanocrystalline phase Ni3P was determined. X-ray diffraction analysis showed that heat treatment produces Ni3P phosphides and, presumably, Ni5P2, the size of which, according to electron microscopy, is 5–50 nm. The influence of the duration of heat treatment on the phase composition and microhardness of coatings is investigated.