In this paper, the room-temperature performance of different optical coupling materials post temperature exposure was tested. The tested couplers included OC431A-LVP, OG0010 optical grease, BLUESIL V-788, and SAINT-GOBAIN BC-630. This was done by subjecting the whole detector with newly applied optical coupling materials to a 2-h temperature exposure—ranging from −20 to 50 °C and then by letting it return to room temperature before collecting a spectrum from a Cs-137 source. The energy resolution at 662 keV was computed as the metric for evaluating the performance. Three trials were run at each coupler–temperature combination. Our results reveal that the performance of all coupling agents do indeed change with temperature after the 2-h exposure. Over all the tested temperature trials, the energy resolution ranged from 11.4 to 14.3% for OC431A-LVP; 10.2 to 14.6% for OG0010; 10 to 13.4% for BLUESIL V-788; and 9.8 to 13.3% for SAINT-GOBAIN BC-630. OC431A-LVP had the lowest variance over the full range, while BC-630 was the most constant for temperatures above 20 °C. Ultraviolet-visible (UV-Vis) spectra experiments were also performed on isolated optical coupling materials to measure the light absorption coefficient. The results show that the temperature-induced variance in light absorption coefficient of each optical coupling materials is one of the reasons for the variance in energy resolution performance. Our findings suggest the need for further investigation into this effect and the recommendation that optical coupling materials need to be selected for the task at hand with greater scrutiny.