Luminescent crystals with high efficiency have huge potential in applications for white light-emitting diodes (LEDs). Herein, organic-inorganic hybrid crystals doped with Mn4+, [N(CH3)4]2XF6:Mn4+ (X = Si, Ge, and Ti), were grown under mild conditions. Their crystal structural evolution was confirmed by single-crystal X-ray diffraction at different temperatures. These crystals exhibit intense red emission with a high external quantum efficiency (73.0% for [N(CH3)4]2TiF6:Mn4+) and good thermal stability. The warm white LEDs were fabricated by combining these red-emitting phosphors with a YAG:Ce3+ ceramic chip. As-grown crystals can significantly optimize the performances of white LEDs (colour rendering index up to 95). Hence, this work provides a new strategy to explore Mn4+-activated organic-inorganic hybrid materials for white LEDs.