The remediation of cadmium (Cd) contaminated soil is challenging for agricultural practices. In this study, a novel vinasse biochar modified by potassium ferrate (K2FeO4) was synthesized to immobilize Cd in agricultural soil. Three biochars i.e., vinasse biochar (BC), KMnO4 modified vinasse biochar (MnBC), and K2FeO4 modified vinasse biochar (FeBC) were applied to compare their efficiencies of Cd immobilization. The results showed that the orders of pH, ash content, and functional groups in different biochar were the same following BC < MnBC < FeBC. Scanning electron microscope images showed that the FeBC has more micropores than MnBC and BC. X-ray diffraction identified manganese oxides and iron oxides within MnBC and FeBC, indicating that Mn and Fe were well loaded on the biochar. In the soil-based pot experiment, both MnBC and FeBC significantly reduced soil available Cd by 23–38% and 36–45% compared with the control, respectively (p < 0.05). In addition, the application of BC, MnBC, and FeBC significantly increased the yield, chlorophyll, and vitamin C of Chinese cabbage (p < 0.05), and decreased its Cd uptake compared with the control. Notably, shoot Cd significantly reduced when 2% FeBC was applied (p < 0.05). Overall, using K2FeO4 to modify vinasse biochar enriched the surface functional groups and minerals as well as reduced Cd availability in soil and its uptake by the plant. Our study showed that K2FeO4 modified vinasse biochar could be used as an ideal amendment for the remediation of Cd-contaminated soil.