This paper investigates the influence of the technological parameters of detonation spraying on the phase composition of NiCr- and Al2O3-based coatings. It was determined that the phase composition of Al2O3 coatings during detonation spraying strongly depends on the barrel filling volume with the gas mixture. The acetylene–oxygen mixture, which is the most frequently used fuel in the detonation spraying of powder materials, was used as a fuel gas. To obtain a ceramic layer based on Al2O3, spraying was performed at an acetylene–oxygen O2/C2H2 mixture ratio of 1.856; the volume of filling of the detonation gun barrel with an explosive gas mixture was 63%. To obtain a NiCr-based metallic layer, spraying was performed at the O2/C2H2 ratio of 1.063; the volume of filling of the detonation gun barrel with an explosive gas mixture was 54%. Based on a study of the effect of the detonation spraying mode on the phase composition of NiCr and Al2O3 coatings, NiCr/NiCr-Al2O3/Al2O3-based multilayer coatings were obtained. Mixtures of NiCr/Al2O3 powders with different component ratios were used to obtain multilayer gradient coatings. The structural-phase composition, mechanical and tribological properties of multilayer gradient metal–ceramic coatings in which the content of the ceramic phase changes smoothly along the depth were experimentally investigated. Three-, five- and six-layer gradient coatings were obtained by alternating metallic (NiCr) and ceramic (Al2O3) layers. The phase composition of all coatings was found to correspond to the removal of information from a depth of 20–30 μm. It was determined that the five-layer gradient coating, consisting of the lower metal layer (NiCr), the upper ceramic layer (Al2O3) and the transition layer of the mechanical mixture of metal and ceramics, is characterized by significantly higher hardness (15.9 GPa), wear resistance and adhesion strength.