In the present study, the effect of alumina (Al2O3) nano-powder was investigated for the electrical discharge machining (EDM) of a Nitinol shape memory alloy (SMA). In addition to the nano-powder concentration, other parameters of pulse-on-time (Ton), pulse-off-time (Toff), and current were selected for the performance measures of the material removal rate (MRR), surface roughness (SR), and tool wear rate (TWR) of Nitinol SMA. The significance of the design variables on all the output measures was analyzed through an analysis of variance (ANOVA). The regression model term has significantly impacted the developed model terms for all the selected measures. In the case of individual variables, Al2O3 powder concentration (PC), Toff, and Ton had significantly impacted MRR, TWR, and SR measures, respectively. The influence of EDM variables were studied through main effect plots. The teaching–learning-based optimization (TLBO) technique was implemented to find an optimal parametric setting for attaining the desired levels of all the performance measures. Pursuant to this, the optimal parametric settings of current at 24 A, PC at 4 g/L, Toff at 10 µs, and Ton of 4 µs have shown optimal input parameters of 43.57 mg/min for MRR, 6.478 mg/min for TWR, and 3.73 µm for SR. These results from the TLBO technique were validated by performing the experiments at the optimal parametric settings of the EDM process. By considering the different user and application requirements, 40 Pareto points with unique solutions were generated. Lastly, scanning electron microscopy (SEM) performed the machined surface analysis. The authors consider this to be very beneficial in the nano-powder-mixed EDM process for appropriate manufacturing operations.