Many Mn 4+ ion-doped Ca 3 La 2 W 2 O 12 phosphors were produced using the conventional high-temperature solid-phase method. The microstructure, luminescence properties, quantum yield, and fluorescence lifetime of Ca 3 La 2 W 2 O 12 :xMn 4+ phosphors were systematically researched by XRD, fluorescence spectrometer, and SEM. In 300–550 nm, Ca 3 La 2 W 2 O 12 :xMn 4+ phosphor has an influential broad excitation band. In 650–800 nm, there is an emission peak at 715 nm, which corresponds to the 2 E g → 4 A 2g energy level transition of Mn 4+ ion. With the increase of the doping concentration of Mn 4+ ions, the luminescence intensity first increases and then decreases. When the Mn 4+ concentration is x = 0.07, the concentration quenching appears due to the electric dipole-electric quadrupole effect. The influences of various Mn sources on the luminescence performance of Ca 3 La 2 W 2 O 12 :0.07Mn 4+ phosphor were investigated. The outcomes show that the emission spectrum of the Ca 3 La 2 W 2 O 12 :xMn 4+ phosphor was well-matched with the absorption band of the plant photosensitive pigments P R and P FR . As a result, Ca 3 La 2 W 2 O 12 :xMn 4+ phosphors are extremely promising applications in promoting plant growth, flowering, and fruiting. • The influence of different sources of manganese on the luminescence properties of Ca 3 La 2 W 2 O 12 :xMn 4+ phosphors was discussed. • The Ca 3 La 2 W 2 O 12 :xMn 4+ deep-red phosphors are promising for use in plant cultivation lighting fields. • The crystal field environment of Mn 4+ ions was analyzed, and the Mn 4+ ions are located in the strong crystal field. • The Ca 3 La 2 W 2 O 12 :0.07Mn 4+ phosphor color coordinate is (0.733, 0.267) in the red area, and the quantum yield is up to 51.3%.