The development of high-performance phosphors is required for phosphor-converted white light-emitting diodes. However, most approaches are unable to achieve optimum emission intensity and thermal quenching simultaneously. Here, a series of CaAlSiN3:Eu2+ (CASN:Eu2+) red-emitting phosphors doped with B were synthesized using field-assisted sintering technology. Compared with CASN:Eu2+, the B-doped phosphor exhibited high external quantum efficiency (EQE) and good thermal quenching performance. With boron doping, the EQE of CaAlSiN3:Eu2+ shows an obvious growth, increasing from 48.83% to 70.68%. Meanwhile, thermal quenching performance has also been greatly improved, which is strongly associated with the band structure of Eu2+ and the crystal structure of CASN. The location of B in the crystal lattice was studied and the mechanism of improving thermal quenching via B doping was discussed in detail. Finally, a white LED fabricated by the combination of a GaN blue chip (450 nm) with the as-synthesized red phosphors and Y-3(Al, Ga)(5)O-12:Ce3+ green phosphors (531 nm), shows a high color rendering index (Ra =91.6). This study offers a novel method to improve luminescence properties of CASN:Eu2+ red-emitting phosphors, which may broaden their application in solid-state lighting devices.