A fundamental understanding and control of impurity incorporation and charge carrier recombination are critical for emerging ScxAl1−xN electronics, optoelectronics, and photonics. We report on the photoluminescence properties of ScxAl1−xN grown by plasma-assisted molecular beam epitaxy with varying growth temperatures and Sc contents. Bright and broad emission comprising a dominant peak at ∼3.52 eV and a weak peak at ∼2.90 eV was observed in Sc0.05Al0.95N. The origin of the ∼3.52 eV emission line is attributed to charge carrier recombination from the localized excited state of (Vcation-ON)2−/− to its ground state, whereas the second peak at ∼2.90 eV results from charge carrier recombination of isolated Vcation3−/2− to the valence band. We further show that oxygen defect-related emission can be significantly suppressed by increasing growth temperature. This work sheds light on the recombination dynamics of photoexcited carriers in ScxAl1−xN and further offers insight into how to improve the optical and electrical properties of ScxAl1−xN that are relevant for a broad range of applications.