An intermediate connector of Cs2CO3/Al/MoO3 used in tandem organic light-emitting diodes (OLEDs) was investigated in this work. Here, an ultrathin Cs2CO3/Al was used as an electron-injection layer (EIL) from MoO3 to the adjacent electron transporting layer (ETL). To verify the function of this intermediate connector, the device performances were evaluated through current density-voltage-luminance characteristics, current density-efficiency curves, and EL spectra. Additionally, the effect of photon energy on carriers behavior in the Cs2CO3/Al/MoO3 connector is also estimated. The electrical properties and EL spectra of tandem OLEDs show that the Cs2CO3/Al/MoO3 can function well for charge generation and transport, and the current density-voltage curves of Cs2CO3/Al/MoO3 based special multilayer device shows the photovoltaic effect as a photovoltaic cell.