Caramel color is a food colorant widely used in the fermented beverage industries. In this context, this study investigated the effects of caramel color on the quality of Huangjiu in terms of color, physicochemical properties, sensory characteristics, and the release of volatile compounds. The results showed that Class IV caramel colors with the highest color intensity had the lowest coloring ability in Huangjiu due to precipitation. Caramel colors significantly affected the total sugar, titratable acidity, and amino nitrogen of Huangjiu. Sensory analyses indicated that the three classes of caramel color significantly affected 10 sensory attributes and the aroma release of Huangjiu. The headspace concentration of the 40 volatile organic compounds (VOCs) in Huangjiu changed significantly. Principal component analysis (PCA) and cluster analysis showed that Classes I and III caramel colors had similar effects on the VOCs in Huangjiu. Partial least-squares discriminant analysis (PLS-DA) showed that 9 compounds made important contributions to distinguishing different classes of caramel-colored Huangjiu samples. This study provides a theoretical foundation for the scientific application of caramel color in Huangjiu and other fermented food industries.