This paper reports on the results of an investigation into the nature of photoluminescence upconversion at GaAs/InGaP 2 interfaces. Using a dual-beam excitation experiment, we demonstrate that the upconversion in our sample proceeds via a sequential two-photon optical absorption mechanism. Measurements of photoluminescence and upconversion photoluminescence revealed evidence of the spatial localization of carriers in the InGaP 2 material, arising from partial ordering of the InGaP 2 . We also observed the excitation of a two-dimensional electron gas at the GaAs/InGaP 2 heterojunction that manifests as a high-energy shoulder in the GaAs photoluminescence spectrum. Furthermore, the results of upconversion photoluminescence excitation spectroscopy demonstrate that the photon energy onset of upconversion luminescence coincides with the energy of the two-dimensional electron gas at the GaAs/InGaP 2 interface, suggesting that charge accumulation at the interface can play a crucial role in the upconversion process.