The co-pyrolysis of oily sludge with biomass to prepare carbon materials is not only an effective way to mitigate oily sludge pollution, but it is also a method of obtaining carbon materials. In this study, a carbon material (OS-CS AC) was obtained by the direct co-pyrolysis of oily sludge (OS) and corn stalks (CS) and then applied to Cr(VI) removal. According to the hydroxy and carboxy masking experiments and the characterization of OS-CS AC by FT-IR, SEM, XPS, XRD, and N2 physical adsorption–desorption, Cr(VI) can be adsorbed efficiently through pore filling, the surface oxygen-containing functional groups can promote the reduction of Cr(VI) to Cr(III) through electron donors, and the greater the electrostatic attraction between the electron-donating functional groups of OS-CS AC and the Cr(VI) is, the stronger the ability to remove Cr(VI). In addition, the removal process was discussed, and the results indicated that the McKay kinetic model, Langmuir isotherm model and Van't Hoff thermodynamic model were the most suitable models for removal. The main factors affecting the removal of Cr(VI) were discussed, and the removal of Cr(VI) reached 99.14%, which gives a comprehensive utilization way of oily sludge and corn stalks.