The mechanism of the material destruction under discharge pulses and material removal mechanism based on the thermochemical nature of the electrical erosion during electrical discharge machining of conductive materials were researched. The experiments were conducted for two structural materials used in the aerospace industry, namely austenite anticorrosion X10CrNiTi18-10 (12kH18N10T) steel and 2024 (D16) duralumin, machined by a brass tool of 0.25 mm in diameter in a deionized water medium. The optimized wire electrical discharge machining factors, measured discharge gaps (recommended offset is 170–175 µm and 195–199 µm, respectively), X-ray photoelectron spectroscopy for both types of materials are reported. Elemental analysis showed the presence of metallic Zn, CuO, iron oxides, chromium oxides, and 58.07% carbides (precipitation and normal atmospheric contamination) for steel and the presence of metallic Zn, CuO, ZnO, aluminum oxide, and 40.37% carbides (contamination) for duralumin. For the first time, calculating the thermochemistry parameters for reactions of Zn(OH)2, ZnO, and NiO formation was produced. The ability of Ni of chrome–nickel steel to interact with Zn of brass electrode was thermochemically proved. The standard enthalpy of the Ni5Zn21 intermetallic compound formation (erosion dust) ΔH0298 is −225.96 kJ/mol; the entropy of the crystalline phase Scint is 424.64 J/(mol·K).