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Chemical shrinkage in thermosetting polymers drives residual stress development and induces residual deformation in composite materials. Accurate characterization of chemical shrinkage during curing is therefore vital to minimize residual stresses through process modeling and optimize composite performance. This work introduces a novel methodology to measure the pre- and post-gelation chemical shrinkage of an epoxy resin using three-dimensional digital image correlation (3D-DIC). Differential scanning calorimetry (DSC) is employed to calculate reaction kinetics and correlate chemical shrinkage with the degree of cure. Rheology experiments are conducted to quantify gelation and validate post-gelation. 3D-DIC post-gelation results show excellent agreement with rheology. Pre-gelation results show the effect of the in-situ curing in the proximity of constraints on the global strain behavior. This work introduced an innovative approach to characterize the chemical shrinkage of thermosets during curing, which will enable accurate residual stress prediction for enhancing thermoset composite performance and provide insight into the in-situ polymer behavior during processing.