This work develops a simple and practical process for separation of acrylonitrile–butadienestyrene (ABS) and polystyrene (PS) waste plastics by froth flotation after surface modification using potassium ferrate. ABS plastics containing brominated flame retardants (BFRs) can release hazardous emissions during the process of disposal. Moreover, ABS and PS are typical styrene plastics with similar properties, posing severe restrictions on their separation for recycling. Thus, potassium ferrate modification was investigated and found to decrease selectively the floatability of ABS, providing available process for separation of ABS and PS. Contact angle measurements, FT-IR, XPS and SEM characterization analysis confirmed that potassium ferrate modification can induce the desired changes in the surface properties of ABS. With consideration to separation of ABS and PS, the optimum conditions are potassium ferrate concentration 0.15 M/L, modification time 15 min, temperature 60 °C, stirring rate 200 rpm, frother concentration 14.50 mg/L and flotation time 2 min. Under optimum conditions, separation of ABS and PS with different mixing ratios was accomplished with a recovery and purity of 98.60% and 98.62% respectively. Moreover, reusing of potassium ferrate solution is feasible, further eliminating emissions and cost of this process. Consequently, surface modification using potassium ferrate can be applied for facilitating flotation separation of ABS and PS waste plastics.