With suitable electron-phonon coupling strength, a near-unity broadband photoluminescence quantum yield (PLQY) can be achieved in organic-inorganic hybrid metal halides (OIHMHs) via self-trapped exciton (STE) emission. However, it is still challenging to obtain high-quality red emission from OIHMHs with a desirable emission wavelength and high chemical stability, which hinders their practical application in high-performance displays, plant-growth lighting, and biomedical imaging. Herein, a series of hafnium-based zero-dimensional (TPP)2HfCl6·4C2H3N (TPP: tetraphenylphosphonium) single crystals with different Sb3+ doping levels are synthesized. The Sb3+-doped (TPP)2HfCl6·4C2H3N shows dual-band red emission with a full width at half-maximum of 178 nm and a high PLQY of 91.09%. This broad dual-band emission originates from dopant-induced extrinsic free excitons and STEs. Furthermore, (TPP)2HfCl6·4C2H3N:Sb3+ was employed as a luminescence converter in a light-emitting diode (LED) for plant growth regulation. A correlated color temperature of 4055 K and a color rendering index of 82.13 were achieved upon excitation of the LED at 365 nm. These results provide fundamental perspectives on the emission behavior of Sb3+-doped OIHMHs and illustrate their promise for use in plant-growth lighting.