Tensile-strained GaAsP/GaInP single quantum well (QW) laser diode (LD) structures have been grown by low-pressure metal organic chemical vapor deposition (LP-MOCVD) and related photoluminescence (PL) properties have been investigated in detail. The samples have the same well thickness of 16 nm but different P compositions in a GaAsP QW. Two peaks in roomtemperature (RT) PL spectra are observed for samples with a P composition larger than 0.10. Temperature-and excitationpower-dependent PL spectra have been measured for a sample with a P composition of 0.15. It is found that the two peaks have a 35 meV energy separation independent of temperature and only the low-energy peak exists below 85 K. Additionally, both peak intensities exhibit a monotonous increase as excitation power increases. Analyses indicate that the two peaks arise from the intrinsic-exciton recombination mechanisms of electron-heavy hole (e-hh) and electron-light hole (e-lh). A theoretical calculation based on model-solid theory, taking into account the spin-orbit splitting energy, shows good agreement with our experimental results. The temperature dependence of PL intensity ratio is well explained using the spontaneous emission theory for e-lh and e-hh transitions, from which the ratio can be characterized mainly by the energy separation between the hh and lh states.