Traditional PV/energy storage generating system is composed of photovoltaic array and storage cell, which easily suffers from PV cell’s shadow effect and energy storage cell’s equalization. Therefore this paper proposes a novel PV/energy storage generating system consist of single PV cell/single energy storage cell. In this generating system, single PV cell and single energy storage cell having the matched voltage and capacity with the former constitute PV/energy storage module. A certain number of modules are connected in series to form a series branch, which is connected to the DC bus by boosting DC/DC converter. Series branches are connected in parallel to supply power to DC load or to AC load via inverter. The PV/energy storage module has 5 operating modes, which are switched autonomously by monitoring PV cell and energy storage cell’s voltage and current. The series branch, containing PV/energy module switch-in and switch -off, is controlled by monitoring the input voltage of DC/DC converter. This paper also proposes a method of choosing the PV cell’s voltage parameter in the proposed module based on the criteria of utilization efficiency of solar energy. At last, the simulation model of the new generating system is built, which shows the feasibility and effectiveness of the system theoretically. This work is supported by National Natural Science Foundation of China (No. 51307144).