Abstract Ti6Al4V is the most widely used materials in aerospace, medical, nuclear power and other fields. However, due to its unique properties such as low thermal conductivity, titanium alloy poses challenges in machining processes. Electrical discharge milling (EDM) is a machining method that utilizes the electrical corrosion phenomenon of pulsed spark discharge between two electrodes to remove materials, which is highly suitable for the machining of Ti6Al4V. This paper investigates a mixed powder EDM approach for titanium alloy using a graphene solution medium known for its green and sustainable characteristics. Compared to conventional deionized water medium processing which without powder particles, the material removal rate can be increased by 50%, the surface hardness after processing was 2.5 times higher than that of the substrate, the electrode wear rate could be reduced by 40%, the surface roughness values were reduced by more than 20%. Besides that, the micro-cracks and micro-pores on the workpiece surface can be significantly reduced. Subsequently, single factor experiments and orthogonal experiments were conducted using material removal rate, electrode wear rate, and surface roughness as process indicators. The influence of processing parameters on process indicators was investigated based on optimal selection method and analysis of variance (ANOVA). Finally, the optimized parameters in graphene solution mixed powder EDM for Ti6Al4V were obtained. When using the process combination A3B3C1D2, the maximum MRR can be obtained.