The internal behaviors of carriers in InGaAsP single-junction solar cell are investigated by using electroluminescence (EL) measurements. Two emission peaks can be observed in current-dependent electroluminescence spectra at low temperatures, and carrier localization exists for both peaks under low excitation. The trends of power index α extracted from excitation-dependent EL spectra at different temperatures imply that there exists a competition between Shockley–Read–Hall recombination and Auger recombination. Auger recombination becomes dominant at high temperatures, which is probably responsible for the lower current density of InGaAsP solar cell. Besides, the anomalous “S-shape” tendency with the temperature of band-edge peak position can be attributed to potential fluctuation and carrier redistribution, demonstrating delocalization, transfer, and redistribution of carriers in the continuum band-edge. Furthermore, the strong reduction of activation energy at high excitations indicates that electrons and holes escaped independently, and the faster-escaping carriers are holes.