The excited-state energy transfer widely exists in mixed-material systems and devices. The modulation of an electric field on the energy transfer in photoluminescence has been demonstrated. However, to date, no studies on the electric-field modulation of the excited-state energy transfer in organic optoelectronic devices have been reported. Herein, we investigate the effect of an electric field on the energy transfer in the poly(N-vinylcarbazole) (PVK) thin films doped with iridium(III)[bis(4,6-difluorophenyl)pyridinato-N,C^2′]-tetrakis(1-pyrazolyl)borate (Fir6) and 5,6,11,12-tetraphenylnaphthacene (rubrene) (PVK:Fir6:rubrene) and the corresponding light-emitting diodes. Combined with the Onsager model describing electric-field enhanced exciton dissociation, we find that the electric field increases the rate of Dexter energy transfer from Fir6 to rubrene in the films and the diodes. The voltage-dependent color shift in the PVK:Fir6:rubrene light-emitting diodes can be explained by the electric-field enhanced Dexter energy transfer from Fir6 to rubrene. Our findings are important for the control of energy transfer process in organic optoelectronic devices by an electric field for desirable applications.