In DC microgrids, a large-capacity hybrid energy storage system (HESS) is introduced to eliminate variable fluctuations of distributed source powers and load powers. Aiming at improving disturbance immunity and decreasing adjustment time, this paper proposes active disturbance rejection control (ADRC) combined with improved MPC for n + 1 parallel converters of large-capacity hybrid energy storage systems. ADRC is utilized in outer voltage control loops, and improved MPC is employed in inner current control loops of n battery converters. Droop control is adopted to obtain power distribution between n battery converters, and a DC bus voltage compensator is used to compensate voltage deviations and maintain constant DC bus voltage. The low-pass filter (LPF) is adopted to obtain high-frequency power as the reference for the supercapacitor converter, ADRC is also utilized in the outer power control loop, and MPC is employed in the inner current control loop. Compared with traditional observers, the voltage expansion state observer of the proposed ADRC control is independent of the system model and parameters and consequently has strong disturbance immunity, and significantly reduces voltage overshoots during power fluctuations. The MPC-based inner current control loops of n + 1 converters accelerate current response speed and significantly decrease switching losses. Simulation and experimental results indicate that utilizing the proposed control strategies, large-capacity HESS has stronger anti-interference ability, shorter regulation time, smaller switching loss, and simultaneously maintains the stability of the DC bus voltage.