Ferrate as an environmentally friendly oxidant has been widely used in the environmental remediation and versatile functionalization of carbon-based materials. In this study, we investigated its ability to induce surface wettability of polymers and its emerging applications in separating mixed plastics through flotation for recycling. It was found that ferrate (VI) formed oxygen-containing groups on the surface of polycarbonates (PCs) by selectively oxidizing the sp³-hybridized carbon atoms into hydroxyl and carboxyl moieties, in addition to introducing nanoscale iron oxides. This facilitated the selective hydrophilization of PC with a water contact angle of 60.7° but did not clearly affect the surface wettability of polyvinyl chloride (PVC). This difference in surface wettability highlighted the distinct floatability properties of PC and PVC, which can be utilized to separate mixtures of these plastics with the aid of flotation. A central composite design (CCD) utilizing response surface methodology (RSM) was applied to model ferrate oxidation and to optimize flotation. Under the optimized conditions, mixtures of PC and PVC were efficiently separated with recovery and purity values of more than 99.8 ± 0.3%. Our findings provide a rational understanding of polymer wettability tailoring and expand its emerging applications in waste plastic recycling to address environmental problems.