To solve the problems of large switching losses and the need for large-capacity electrolytic capacitances in three-phase DC/AC on-board chargers for vehicle-to-grid (V2G) applications, this paper proposes a single-stage bidirectional high-frequency isolated converter that eliminates the need for large-capacity capacitances. Combined with the proposed modulation scheme, it can theoretically reduce the switching loss by about two-thirds with the three-phase converter compared with the conventional modulation scheme, improving the converter’s operating efficiency and power density. Firstly, based on the characteristics of the proposed topology, a hybrid modulation scheme is proposed, which combines a phase-shift modulation scheme based on double modulation waves and a sawtooth carrier with a 1/3 modulation scheme, and the theoretical feasibility of the hybrid modulation scheme is verified using a mathematical modeling equation. Secondly, this paper provides a detailed analysis of the four operating modes of the two full-bridge circuits and the commutation process of the three-phase converter within 1/6 of the fundamental frequency cycle (P1 modulation interval). Then, the control strategy is given for the constant-current and constant-voltage charging and constant-current discharging for electric vehicle batteries. Finally, simulation results verify the correctness of the proposed topology and modulation scheme in vehicle–grid interaction.