We demonstrate tandem organic light-emitting diodes (TOLEDs) with excellent performance using Al and MoO3 buffer-modified C60/pentacene as charge generation layer (CGL). Al and MoO3 were used as the electron and hole in-jection layers of C60/pentacene CGL, respectively. Green phosphorescence TOLEDs with the structure of ITO/NPB/mCP:Ir(ppy)3/TPBi/Al/C60/pentacene/MoO3/NPB/mCP:Ir(ppy)3/TPBi/Cs2CO3/Al were fabricated. The re-sults show that the inserted Al and MoO3 can effectively increase the charge injection capacity of organic CGL, re-sulting the improvement of luminance and current efficiency of TOLEDs. The turn-on voltage of TOLEDs is much lower than that of single-unit device, and the current efficiency is more than 2 times larger than that of the single-unit device. TOLEDs can exhibit excellent photoelectric performance when the thicknesses of Al, C60, pentacene and MoO3 are 3 nm, 15 nm, 25 nm and 1 nm, respectively. The maximum luminance and current efficiency are 7 920.0 cd/m2 and 16.4 cd/A, respectively. This work is significant to build new CGL structures for realizing high-performance TOLEDs.