Due to inherent properties of Ti-6Al-4V alloy, it is being used in the application of fuel injector nozzle for diesel engine, aerospace and marine industries. Since the electrochemical micromachining process involves the no heat-affected zone, no tool wear, stress- and burr-free process compared to other micromachining processes, it is widely used in the manufacturing field to fabricate complex shape and die. Hence, it is highly important to compute the optimum input parameters for enhancing the machining characteristics in such machining process. In this study, an attempt has been made to find the influence of the process parameters and optimize the parameters on machining α–β titanium alloy using Taguchi-grey relational analysis. Since applied voltage, micro-tool feed rate, electrolyte concentration and duty cycle have vital role in the process, these parameters have been chosen as the input parameters to evaluate the performance measures such as material removal rate, surface roughness and overcut in this study. From the experimental results, it has been found that micro-tool feed rate has more influence due to its importance in maintaining inter electrode gap to avoid micro-spark generation. It has also been found that lower electrolyte concentration with lower duty cycle produces lower surface roughness with better circularity on machining α–β titanium alloy. The optimum combination has been found using Taguchi-grey relational analysis and verified from confirmation test. It has also been inferred that the multi-response characteristics such as material removal rate, surface roughness and overcut can be effectively improved through the grey relational analysis.