The deleterious innate attribute of Ti6Al4V, the workhorse material among the alloy series of titanium is its incompetent tribo-behavior. Infinite surface modification techniques, viz., the accretion of adherent appendage layers, diffusion hardening, infusion of residual stresses, microstructural evolution, and phase transformations were attempted to enhance the wear resistance of the alloy. The need lies to establish a bridge between the indigenous material properties and the tribo-characteristics of Ti6Al4V so that the enforced improvement techniques can raise the barriers of its applicability. A critical review of the microstructural transitions, mechanisms governing tribo-behavior and the parametric conditions leading to material removal at dry sliding conditions of Ti6Al4V, falls under the scope of this manuscript. Hence, the prime focus of the approach is to impart a clear-cut perception of the minute variations in mechanical, metallurgical, and tribological characteristics of the alloy at interactive instances with distinct counter-body surfaces.