In the present scenario, electrochemical arc machining (ECAM) (hybrid of electric discharge erosion and electrochemical dissolution) is an evolving procedure for difficulty in machining the materials due to constraints of existing processes. This research aims to investigate the machinability of Ni[Formula: see text]Ti alloy through electrochemical arc drilling using molybdenum electrode. Electrolyte concentration (ethanol with ethylene glycol and sodium chloride), supply voltage, and tool rotation are considered as the variable factors to evaluate the ECAM performance characteristics in drilling blind hole operation concerning overcut (OC), tool wear rate (TWR) and materials removal rate (MRR). Consequently, response surface methodology is implemented for predictive modeling of various performance characteristics. Finally, multi-objective optimization through desirability function approach (DFA) has produced a set of optimal parameters to improve the productivity along with the accuracy, which is the prime requirement for the industrial applicability of the ECAM process. Results demonstrated that supply voltage is the influential key factor for improvement of machining rate. Scanning electron microscope (SEM) photographs revealed the development of heat affected zone (HAZ), white layer, melted droplet, craters, re-solidified material, ridge-rich surface and voids as well as cavities around the end-boundary surfaces of a blind hole. Composition analysis through energy dispersive spectroscopy (EDS) indicated the oxygen content on the machined surface because electrolyte breakdown causes oxidation to take place at elevated temperatures across the machining zone. Moreover, carbide precipitation like TiC was found in the melting zone of the drilled hole, as revealed by X-ray diffraction (XRD) analyses, which has the affinity to reduce the SMA properties in HAZ.