This study examines the thermal behavior of a laser ignited thermite composed of aluminum and bismuth trioxide. Temperature data were collected during the reaction using a four-color pyrometer and a high-speed color camera modified for thermography. The two diagnostics were arranged to collect data simultaneously, with similar fields of view and with similar data acquisition rates, so that the two techniques could be directly compared. Results show that at initial and final stages of the reaction, a lower signal-to-noise ratio affects the accuracy of the measured temperatures. Both diagnostics captured the same trends in transient thermal behavior, but the average temperatures measured with thermography were about 750 K higher than those from the pyrometer. This difference was attributed to the lower dynamic range of the thermography camera’s image sensor, which was unable to resolve cooler temperatures in the field of view as well as the photomultiplier tube sensors in the pyrometer. Overall, while the camera could not accurately capture the average temperature of a scene, its ability to capture peak temperatures and spatial data make it the preferred method for tracking thermal behavior in thermite reactions.