Developing efficient and stable red phosphor has always been considered as important academic research of LED plant-growth lamps. In this study, Mn4+-activated double perovskite red phosphors, A2BB’O6:Mn4+ (A = Sr, Ba; B = Lu, Gd; B’ = Nb, Ta), were successfully synthesized by solid-phase method. To elucidate the structure-activity relationship between the double perovskite structure and the luminescence of Mn4+, the crystal structure, electronic structure and luminescence properties of Sr2LuNbO6:Mn4+ were first studied in detail using X-ray powder diffraction data, density functional theory calculations and spectroscopy data. The coordination environment of Mn4+ was analyzed by investigating the crystal-field parameters, Racah parameters and nephelauxetic parameter. Then, the effect of structural evolution on the luminescence of Mn4+ was investigated by regulating the local coordination environment of Mn4+ through cationic modification. The results demonstrate that Mn4+ enters the octahedral lattice site with a strong crystal field and covalent environment, which can be excited by a near-ultraviolet LED chip to emit narrow-band far-red light in the double perovskite oxides. Moreover, the Mn–O bond length, octahedral distortion and crystal-system type all affect the luminescence of Mn4+. This systemic development provides some guidance for the exploration of novel Mn4+-activated double perovskite red phosphors.