Control of carrier lifetimes in nitrogen (N)-doped n-type 4H-SiC epilayers was attempted by intentional boron (B) doping. Doping concentrations of B were controlled to be within 1015–1018 cm−3 by varying the triethyl boron flow rate during epitaxial growth. Time-resolved photoluminescence measurements for the band edge luminescence of the N + B-doped epilayer showed a fast decay time of less than 30 ns under a low injection level at 300 K, while a slow decay component was observed at elevated temperatures of 423–523 K. To understand the mechanism of carrier capture and recombination in N + B-doped 4H-SiC, excess carrier decay curves were simulated by solving rate equations with a simple model. As an effective “recombination enhancing layer,” the 1.6-μm-thick N + B-doped (N: 4 × 1018 cm−3, B: 7 × 1017 cm−3) buffer layer in the PiN diode showed increased intensity of D center-related electroluminescence with increasing injected hole concentrations and prevented the formation of stacking faults from basal plane dislocations in the substrate even at the injection level of 1 × 1016 cm−3 at the interface between the drift and buffer layers.