The energy transfer from Yb 3þ to Er 3þ ions under electrical excitation which enhances the Er-related 1531 nm electroluminescence is evidenced, within the nanolaminate Yb,Er co-doped Al 2 O 3 films fabricated by atomic layer deposition. The light-emitting devices based on these nanolaminates present an external quantum efficiency up to 24% and the power efficiency of 2.8Â10 À3 , %60% higher than the solely Er-doped Al 2 O 3 device. The decay dynamics also support, with the radiative lifetime of the Yb 3þ emission reduced while that of Er 3þ emission rises. The Er 3þ and Yb 3þ ions are impact-excited by hot electrons, which stem from Poole-Frenkel conduction mechanism in Al 2 O 3 matrix. This work certifies the potential of sensitizing Er 3þ ions by the adjacent Yb 3þ ions under electrical excitation, and applications of the rare earth-doped nanolaminates in silicon-based optoelectronics.