Quaternary powder mixtures yNi–20Cr–1.5Al–xTiCp (y = 78.5, 73.5, 68.5; x = 0, 5, 10) were deposited on ferritic 10CrMo9–10 steel to form on plates ex-situ composite coatings with austenitic-based matrix. Plasma deposition was carried out with various parameters to obtain eight variants. The microstructure, chemical composition, phase constitution, phase transformation temperatures, and microhardness of the two reference TiCp-free coatings and six ex-situ composites were investigated by X-ray diffraction, scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, thermodynamic simulation, and Vickers microhardness measurements. All composites had an austenite matrix with lattice parameter a = 3.5891–3.6062 Å, calculated according to the Nelson–Riley extrapolation. Microstructural observations revealed irregular distribution of TiCp in the composites. Large particles generally occurred near the external surface due to the acting buoyancy effect, whereas in the interior smaller particles, with an equivalent radius around 0.2–0.6 μm, were present. Due to initial differences in the chemical composition of powder mixtures and also subsequent intensive mixing with the low-alloy steel in the liquid pool, the matrix of the composites was characterized by various chemical compositions with a dominating iron concentration. Interaction of TiCp with matrix during deposition led to the formation of nano-precipitates of M23C6 carbides at the interfaces. Based on the ThermoCalc simulation, the highest solidus and liquidus temperatures of the matrix were calculated to be for the composite fabricated by deposition of 73.5Ni–20Cr–1.5Al–5TiCp powder mixture at I = 130 A. The mean microhardness of the TiCp-free coatings was in the range 138–146 μHV0.1, whereas composites had hardnesses at least 50% higher, depending on the initial content of TiCp.