Electrical Discharge Machining (EDM) is one of the most popular non-conventional machining processes that are being used in many high precision manufacturing industries. To increase the EDM performance, a hybrid technique, namely, powder mixed electrical discharge machining (EDM) (PMEDM) is generally used for getting more precise requirements. In this study, an experimental investigation is carried out in order to explore the machining performance of the PMEDM process on Ti-6Al-4V alloy using copper (Cu) powder in the EDM oil dielectric. Taguchi’s L18 orthogonal array design has been utilized for design of experiments and the analysis of variance (ANOVA) has been performed with the help of Minitab-19 software. The optimal parametric setting of Cu powder mixed EDM has been found utilizing the Taguchi - Grey Relational Analysis (GRA) integrated approach and also validation of optimal parametric setting is done through experimentation. It is a novel approach for machining Ti-6Al-4V alloy by this PMEDM technique in which the surface quality has been improved significantly with the addition of suitable amount of Cu powder into the dielectric medium.