The coefficient of thermal expansion (CTE) is a physical quantity that indicates the thermal expansion value of a material upon heating. For advanced thermal management, the accurate and immediate determination of the CTE of packaging materials is gaining importance because the demand for high-power lighting-emitting diodes (LEDs) is currently increasing. In this study, we used optical coherence tomography (OCT) to measure the CTE of an InGaN-based (λ = 450 nm) high-power LED encapsulated in polystyrene resin. The distances between individual interfaces of the OCT images were observed and recorded to derive the instantaneous CTE of the packaged LED under different injected currents. The LED junction temperature at different injected currents was established with the forward voltage method. Accordingly, the measured instantaneous CTE of polystyrene resin varied from 5.86 × 10-5 °C-1 to 14.10 × 10-5 °C-1 in the junction temperature range 25-225 °C and exhibited a uniform distribution in an OCT scanning area of 200 × 200 μm. Most importantly, this work validates the hypothesis that OCT can provide an alternative way to directly and nondestructively determine the spatially resolved CTE of the packaged LED device, which offers significant advantages over traditional CTE measurement techniques.