Lead-free halide double perovskites are considered as one of the most promising materials in optoelectronic devices, such as solar cells, photodetectors, and light-emitting diodes (LEDs), due to their environmental friendliness and chemical stability. However, the extremely low photoluminescence quantum yield (PLQY) of self-trapped excitons (STEs) emission from lead-free halide double perovskites impedes their applications. Herein, Sb3+ ions were doped into rare-earth-based double perovskite Cs2NaScCl6 single crystals (SCs), resulting in a large enhancement of PLQY from 12.57% to 87.37%. Moreover, by co-doping Sb3+ and Ho3+ into Cs2NaScCl6 SCs, the emission color can be tuned from blue to red, due to an efficient energy transfer from STEs to Ho3+ ions. Finally, the synthesized sample was used in multicolor LED, which exhibited excellent stability and optical properties. This work not only provides a new strategy for improving the optical properties of Cs2NaScCl6 SCs, but also suggests its potential application in multicolor LEDs.