An integrated approach was developed for investigation of thermal spray coatings with the amorphous-crystalline structure. The new approach combines methods of metallography, differential thermal and X-ray phase analysis, scanning electron microscopy and X-ray microanalysis. This makes it possible to reveal structural, phase and chemical heterogeneity, determine the degree of amorphization of coatings, temperature and heat of crystallization of the amorphous phase during heating. The new integrated approach was used to study amorphous-crystalline coatings of the Ni-P, Fe-Ni-B and Fe-B systems produced by thermal spraying.