ne volume shrinkage during polymerization of a thermoplastic modified epoxy resin undergoing a simultaneous viscoelastic phase separation was investigated for the first time by means of pressure-volume-temperature (PVT) analysis. Varying amounts (0-20%) of poly(styrene-co-acrylonitrile) (SAN) have been incorporated into a high-temperature epoxy-diamine system, diglycidyl ether of bisphenol A (DGEBA)-4,4'-diaminodiphenyl sulfone (DDS) mixture, and subsequently polymerized isothermally at a constant pressure of 10 MPa. Volume shrinkage is highest for the double-phased network-like bicontinuous morphology in the SAN-15% system. Investigation of the epoxy reaction kinetics based on the conversions derived from PVT data established a phase-separation effect on the volume shrinkage behavior in these blends. From subsequent thermal transition studies of various epoxy-DDS/SAN systems, it has been suggested that the behavior of the highly intermixed thermoplastic SAN-rich phase is the key for in situ shrinkage control. Various microscopic characterizations including scanning electron microscopy, atomic force microscopy, and optical microscopy are combined to confirm that the shrinkage behavior is manipulated by a volume shrinkage of the thermoplastic SAN-rich phase undergoing a viscoelastic phase separation during cure. Consequently, a new mechanism for volume shrinkage has been visualized for the in situ polymerization of a thermoplastic-modified epoxy resin.