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Cholesteryl ester liquid crystals exhibit thermochromic properties related to the existence of a twisted nematic phase. When used in applications such as thermal mapping, a color change is often monitored by video cameras. Thus, quantitative methods to evaluate thermochromic behavior (e.g., blue-start, red-start, red-end, color play and bandwidth) from video analysis are desirable. However, obtaining quantitative color measurements from digital images remains a significant technical challenge, especially for highly reflective samples such as liquid crystals (for which ultraviolet–visible (UV–vis) reflectance spectroscopy is typically used). We developed a method to determine thermochromic properties from videos of liquid crystal cooling under polarized light microscopy. We relate observed color transitions to quantifiable changes in the cumulative color difference in the International Commission on Illumination (CIE) L*a*b* color space and validate this method with UV–vis reflectance spectroscopy. The measured thermochromic behavior and associated measurement uncertainties (coefficient of variations) were comparable to UV–vis reflectance measurements.