In this study, the anaerobic sludge withdrawn from thickener in a sewage treatment plant served as the precursor for sludge-based biochar fabrication, which was further modified via sulfur (S) heteroatom doping (i.e., S-BC). The S atom doping resulted in the adjustment of the physicochemical properties towards the carbon material, endowment of abundant functional groups on biochar surface, and increasing the binding sites between biochar and Cr(VI). Compared to the primary biochar (i.e., biochar without heteroatomic doping, named BC), S-BC exhibited a rough surface and possessed remarkable advantages in ash content, specific surface area, and pore volume. The existence of graphene carbon crystal structure for S-BC was confirmed through S-BC by XRD and FTIR analysis. The studies of adsorption kinetics and isotherms showed that pseudo-second-order kinetics and the Langmuir model more fitted the Cr(VI) removal behavior in the presence of S-BC. Therefore, the chemisorption and monolayer adsorption were the primary mechanisms involved in the Cr(VI) removal process. Additionally, XPS analysis results illustrated the aqueous Cr(VI) was efficiently eliminated through the synergistic effect of chemisorption and reduction to Cr(III) in the presence of S-BC. Moreover, S-BC could still achieve the Cr(VI) eliminating efficiency of 85.31% undergoing five cycles with unchanged functional group and crystal structure via FTIR and XRD analysis. Thus, the results of this study may shed light on a new approach for simultaneous economical sludge disposal and the sustainable remediation of the Cr(VI)-contaminated wastewater.