Electric Discharge Machining (EDM) is one of the leading non-conventional machining processes used to machine hard-to-cut materials in wide range of industrial, biomedical, automotive, defense and aerospace applications. EDM is a controlled spark generation process, which is usually used for machining of difficult to cut materials. In this study, experiments were performed on Titanium Alloy (Ti6Al4V) using thin-film multi-wall Carbon Nanotubes (MWCNT) coated electrode and uncoated aluminum electrodes. Morphological and structural investigations of MWCNT coating were performed using Scanning transmission electron microscope (TEM) and Raman spectroscopy. All experiments were designed with Taguchi’s L16 orthogonal array. Each experiment performed under different condition of current, gap voltage and pulse on time. MRR, TWR, SR and OC are studied for each experiment. It was observed that MWCNT coated electrode gives better surface roughness, higher material removal rate, and lower tool wear rate. The experimental result showed that MRR increased by 14.15%, tool wear rate decreased by 23.40%, surface roughness reduced by 22.14 % and overcut reduced by 23.43 % respectively as compared to uncoated aluminum electrodes. All performance responses improved with thin-film MWCNT coated electrode due to magnificent electrical conductivity and chemical stability of CNT. Analysis of Variance (ANOVA) carried out to understand significant process parameters and its contribution in mentioned response variables. Multi-Wall CNT shows better results at high temperature and prevents the tool wear rate. The surface roughness of Ti6Al4V improved with MWCNT coated electrode and it was evident with scanning electron microscope (SEM) images of workpiece. Comparative study of coated and non-coated gives new development of novel electrode tool for electric discharge machining processes.