Advanced technical materials such as Nimonic75 alloys exhibit remarkable properties such, as phase stability, good surface stability, higher resistance to oxidation and corrosion, high strength, and toughness, at raised temperatures. The efficient machining of Nimonic75 is a significant problem for the industrialized sector, limiting the overall impact of these materials. The present work is attentive to the effect of various wire electrodes on the machining performance of Nimonic75 with wire electrical discharge machining. After comparing the performance characteristics of the brass wire and the diffusion annealed Zn-coated brass wire, it was observed that the brass wire deserves to be chosen for machining the Nimonic75 alloy. Experiments have been conducted using the response surface methodology technique and mathematical models developed for the selected output responses. Microstructural and metallurgical alterations at different machining conditions have also been investigated. The outcomes show that while low-discharge energy generates superior surface features, high-discharge energy increases productivity in terms of higher material removal efficiency. However, medium discharge energy moderately impacts the machined surface’s productivity and surface characteristics. The structural analysis of the machined surface revealed a decrease in alloying from high to low discharge energy.