The emergence and establishment of electrical discharge machining (EDM) have aided as a practical solution for the processing of advanced materials, including superalloys, viz. Ti6Al4V, Inconel 718, and Hastelloy. Several primary demerits of the EDM process got overcome by its extended/advanced version; namely, powder mixed electrical discharge machining (PMEDM). The transition from EDM to PMEDM hitherto remains open-ended, as a comprehensive understanding of the latter in the context of process dynamics, the role of added powders/particulates (based on their type and properties), potential to act as a surface modification technique, limitations, and possibilities for future advancements, remains unclear. Hence, this paper contributes an extensive overview of the minute nuances that control EDM and PMEDM process mechanisms, the effect/impact of distinct powder additives (metallics, ceramics, and solid lubes) suspended in the dielectric on the (PMEDM) process efficiency and characteristics of the machined surfaces, and discussions about major domains which can get possibly benefitted through deposition of an alloyed layer. Besides, Ti6Al4V is given more emphasis as the work material (for discussion) alongside with other discrete materials.