A novel method is proposed to simultaneously measure the effective chemical shrinkage and modulus evolutions of advanced polymers during polymerization. The method utilizes glass fiber Bragg grating (FBG) sensors. They are embedded in two uncured cylindrical polymer specimens with different configurations and the Bragg wavelength (BW) shifts are continuously documented during the polymerization process. A theoretical relationship is derived between the BW shifts and the evolution properties, and an inverse numerical procedure to determine the properties from the BW shifts is established. Extensive numerical analyses are conducted to provide general guidelines for selecting an optimum combination of the two specimen configurations. The method is implemented for a high-temperature curing thermosetting polymer. Validity of the proposed method is corroborated by two independent verification experiments: a self-consistency test to verify the measurement accuracy of raw data and a warpage measurement test of a bi-material strip to verify the accuracy of evolution properties.