We present comprehensive first-principles density functional theory (DFT) analyses of the interfacial strength and bonding mechanisms between crystalline and amorphous selenium (Se) with graphene (Gr), a promising duo for energy storage applications. Comparative interface analyses are presented on amorphous silicon (Si) with graphene and crystalline Se with a conventional aluminum (Al) current collector. The interface strengths of monoclinic Se (0.43 J m(-2)) and amorphous Si with graphene (0.41 J m(-2)) are similar in magnitude. While both materials (c-Se, a-Si) are bonded loosely by van der Waals (vdW) forces over graphene, interfacial electron exchange is higher for a-Si/graphene. This is further elaborated by comparing the potential energy step and charge transfer (Delta q) across the graphene interfaces. The interface strength of c-Se on a 3D Al current collector is higher (0.99 J m(-2)), suggesting a stronger adhesion. Amorphous Se with graphene has comparable interface strength (0.34 J m(-2)), but electron exchange in this system is slightly distinct from monoclinic Se. The electronic characteristics and bonding mechanisms are different for monoclinic and amorphous Se with graphene as they activate graphene via surface charge doping divergently. The implications of these interfacial physicochemical attributes on electrode performance have been discussed. Our findings highlight the complex electrochemical phenomena in Se interfaced with graphene, which may profoundly differ from their "free" counterparts.