Flocculation is widely applied for dye wastewater treatment, due to its low cost, high efficiency and convenient operation. However, finding novel flocculant with high performance and low cost is still a challenge. Therefore, a fully characterized bivanadyl capped, highly reduced Keggin polyoxometalate (Et3NH)5[PMoV6MoVI6O40(VIVO)2] (PMoV2) was explored as flocculant for the treatment of simulated cationic dye wastewater. The effect of initial pH, PMoV2 dosage, and concentrations of dyes and inorganic salts on the flocculation rate of methylene blue (MB)/ crystal violet (CV)/rhodamine B (RhB) was investigated. Under the optimum conditions, the flocculation rates of MB, CV and RhB were 99.7%, 99.8% and 99.7% in 5min, respectively. In addition, PMoV2 and dyes could be easily recovered from flocs. PMoV2 exhibited high selectivity for CV in the binary systems of CV-MB and CV-MO. Even after five recycling tests, PMoV2 still kept high flocculation rate of MB/CV/RhB. The possible flocculation mechanisms for MB/CV/RhB single system, and MB-CV and MO-CV binary systems were charge neutralization, charge neutralization and π-π interaction, and charge neutralization and electrostatic interaction, respectively. PMoV2 was better than the reported flocculants in the respect of easy availability and operation conditions, reusability and high flocculation rate. The cost effectiveness, eco-friendly nature and excellent flocculation performance in individual and binary dye systems made PMoV2 competitive in the field of water environment remediation and material development. This is the first report about the flocculation activities of bivanadyl capped, highly reduced Keggin polyoxometalate.