In this study, we developed the MoS2-MgOH2-BiVO4 hybrid via the hydrothermal technique for counter electrode (CE) of dye-sensitized solar cells (DSSC). The prepared samples were confirmed by XRD and FTIR analysis. The optical studies were done by ultraviolet–visible spectra, which confirmed the narrowing bandgap of the MoS2-Mg(OH)2-BiVO4 hybrid. The morphological structure of MoS2 nanorods was turned into MoS2-Mg(OH)2-BiVO4 ternary hybrid hierarchical nanosheets that coexisted with particles. The MoS2-MgOH2-BiVO4 counter electrode and commercial TiO2 photoanode were utilized for constructing the DSSC solar cell. According to the photovoltaic responses of the DSSC, the ternary square-like MoS2-MgOH2-BiVO4 hierarchical nanosheets were 1.48 times more effective than pure MoS2. The charge transfer mechanism of ternary hybrid photovoltaic was investigated and discussed.