Rare-earth oxide materials emit thermal radiation in a narrow spectral region, and can be used for a variety of different high-temperature applications, such as the generation of electricity by thermophotovoltaic conversion of thermal radiation. However, because a detailed understanding of the mechanism of selective emission from rare-earth atoms has so far been missing, attempts to engineer selective emitters have relied mainly on empirical approaches. In this work, we present a new quantum thermodynamic model to describe the mechanisms of thermal pumping and radiative de-excitation in rare-earth oxide materials. By evaluating the effects of the local crystal-field symmetry around a rare-earth ion, this model clearly explains how and why only some of the room-temperature absorption peaks give rise to highly efficient emission bands at high temperature (1,000–1,500 °C). High-temperature emissivity measurements along with photoluminescence and cathodoluminescence results confirm the predictions of the theory.