Abstract Under continuous-wave laser excitation in a lattice-matched In 0.53 Ga 0.47 As/In 0.8 Ga 0.2 As 0.44 P 0.56 multi-quantum-well (MQW) structure, the carrier temperature extracted from photoluminescence rises faster for 405 nm compared with 980 nm excitation, as the injected carrier density increases. Ensemble Monte Carlo simulation of the carrier dynamics in the MQW system shows that this carrier temperature rise is dominated by nonequilibrium LO phonon effects, with the Pauli exclusion having a significant effect at high carrier densities. Further, we find a significant fraction of carriers reside in the satellite L-valleys for 405 nm excitation due to strong intervalley transfer, leading to a cooler steady-state electron temperature in the central valley compared with the case when intervalley transfer is excluded from the model. Good agreement between experiment and simulation has been shown, and detailed analysis has been presented. This study expands our knowledge of the dynamics of the hot carrier population in semiconductors, which can be applied to further limit energy loss in solar cells.