Multiphase composite catalysts can be designed for efficient photocatalytic treatment of organic pollutants in wastewater. Herein, the multiphase ZnO/NiWO4/V2C composite catalysts with dual heterojunction and hierarchically assembled nanoflower structures were constructed via a facile two-step hydrothermal and electrostatic self-assembly method. Utilizing NiWO4 and V2C as co-catalysts, these catalysts effectively degraded cationic dyes, methylene blue (MB) and rhodamine B (RhB) under visible light irradiation. The ZnO/NiWO4/V2C catalyst exhibited higher photocatalytic activity than ZnO in the degradation of MB and RhB, with rate constants of 0.0194 min−1 (a 7.43-fold enhancement) and 0.0176 min−1 (a 3.13-fold enhancement). The higher activity can be attributed to the construction of the double heterojunction using NiWO4 and V2C, which can facilitate efficient electron transport, improve charge separation efficiency, and provide more active sites. After four cycles, the ZnO/NiWO4/V2C catalyst still maintained good stability. Consequently, this work can offer a promising approach for environmental pollution treatment.