The investigation of the formation process of pseudoalloy coatings of the copper–aluminium system under the conditions of electric arc spraying is performed. Regression equations reflecting the dependence of the average particle size of the products of wire spraying, the content of oxides and porosity of the coatings on the wire feed rate, voltage at the electrodes, compressed air consumption and spraying distance are obtained using mathematical planning of the experiment. As determined, the main ways to control the size of the sprayed particles during the simultaneous spraying of copper and aluminium wires is to change the compressed air consumption and heat input into the sprayed materials and gas jet. As a result of studying the structure and phase composition of the spraying products, it is found that in the process of simultaneous spraying of copper and aluminium wires as a result of the interphase interaction of their melts pseudoalloy particles are formed, which are a conglomerate of copper–aluminium. Analysis of the study’s results of coatings formation during the spraying of copper and aluminium wires show that heterogeneous pseudoalloy coatings are formed for the entire selected range of electric arc spraying parameters. The coatings consist of lamellas of the initial components of copper and aluminium with the presence of oxide layers of copper. The coatings also contain admixtures of the intermetallic phases Cu$_9$Al$_4$ and CuAl$_2$, which are formed during the formation of the coating layer on the substrate. The content of oxides in the coatings is in the range of 10–17% vol., the porosity of the coatings is 4–8% vol. As a result of the performed investigation, the ways of controlling the structure and consequently the properties of pseudoalloy copper–aluminium coatings by changing the parameters of electric arc spraying are established.