The steady-state and time-resolved photoluminescence properties of CdSe/CdS heterostructures are studied as a function of temperature from 300 to 600 K. The emission properties of samples are found to behave similarly to bulk CdSe, with the samples maintaining high color purity and a slightly contracting band gap at elevated temperature. Photoluminescence from CdSe/CdS samples is maintained with high stability over prolonged illumination and multiple heating and cooling cycles. Structures synthesized with variation in the core and the shell dimensions show that the preservation of emission intensity at high temperature depends strongly on the microscopic structure of the samples. For samples synthesized by seeded growth, the size of the CdSe core is highly correlated with the fraction of preserved sample photoluminescence intensity at high temperature. Temperature-dependent lifetime data suggest that the core structure predicts the stability of photoluminescence at elevated temperatures by controlling the radiative rate. The rate of electron capture, for which the volume fraction of the core is a structural proxy, underpins the ability for radiative processes to compete with thermally induced nonradiative decay pathways. Heterostructures synthesized below 200 °C using highly reactive organometallic precursors show markedly lower thermal stability than samples prepared by seeded growth at 360 °C, suggesting that the temperature of nanocrystal synthesis has direct consequences for the thermal stability of photoluminescence.