Currently, the study of Mn4+-doped oxide red phosphor is a hot research topic to solve the lack of red component in phosphor-converted whitelight-emitting diodes (pc-WLEDs). In this Article, we designed Gd3+/Nb5+ cation substitution by Bi3+/Mn4+ in Ba2GdNbO6 with double-perovskite structure based on the radius and coordination of the cations through high-temperature solid-state reaction. The phase purity and microstructure of double-perovskite Ba2GdNbO6:Bi3+,Mn4+ phosphors were characterized by X-ray diffraction and scanning electron microscopy examination. The crystal structures were also determined by the Rietveld refinement, and the photoluminescence (PL) properties were systematically studied. Bi3+ and Mn4+ ions can be effectively doped in the Ba2GdNbO6 matrix with an optical band gap of 3.94 eV. Upon 315 nm UV excitation, the Ba2GdNbO6:Bi3+ -> Mn4+ phosphor shows two emission bands at 464 nm from Bi(3+ )and 689 nm from Mn4+, respectively. By the design of Bi3+ -> Mn4+ energy transfer, systematic luminescence tuning from blue to red could be achieved because of spectral overlap between the emission spectrum of Bi3+ and the excitation spectrum of Mn4+. The corresponding mechanism of the Bi3+ -> Mn4+ energy-transfer process was investigated in detail by the fluorescence decays and PL spectra. The red emission intensity of Mn4+ has been greatly improved by Bi3+ Mn4+ energy transfer. Moreover, the phonon vibration and zero phonon line of Mn' were studied through temperature-dependent PL. Finally, a WLED was fabricated using a 460 nm blue chip with a yellow YAG:Ce3+ phosphor and a red Ba2GdNbO6:0.01Bi(3+),0.01Mn(4+) phosphor, which has a low correlated color temperature (3550 K) and a high color rendering index (89.6). The above results imply that the improved red emission phosphors have a potential application in warm pc-WLED lighting.