Synthetic dyes from textile effluents represent a major environmental concern due to their persistence and toxicity. Reactive Black 5 (RB5) is widely used in the textile industry and is commonly applied as a model azo compound in sorption studies. This study comparatively evaluates the sorption performance of raw and carbonized sorbents derived from industrial hemp (Cannabis sativa L.) biowaste using an integrated experimental and theoretical approach. The sorbents were prepared through washing, drying, and phosphoric acid-assisted carbonization followed by pyrolysis. Structural and physicochemical properties were characterized using elemental analysis, FTIR spectroscopy, and SEM microscopy. Sorption performance toward RB5 was investigated through batch kinetic and equilibrium experiments, supported by kinetic (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models) and isotherm (Langmuir, Freundlich, and Temkin) modeling. Molecular docking simulations were performed to provide mechanistic insight into dye–sorbent interactions. Both materials exhibited rapid sorption kinetics, reaching equilibrium within approximately 45 min, with the pseudo-second-order model suggesting that surface-controlled interactions dominate the sorption rate. Molecular modeling, based on extensive conformational sampling, indicated a strong binding affinity between RB5 and cellulose-based structures, primarily associated with hydrogen bonding and other favorable noncovalent interactions. In contrast, graphene-based models revealed sorption governed by π–π interactions and confinement effects, supporting the experimentally observed differences between raw and carbonized sorbents.