The structural changes of poly(vinyl chloride) (PVC) plastisols during mixing of PVC with a plasticizer was investigated; as the temperature was increased, the system was found to transform from a suspension of solid particles in a liquid medium to a swollen gel and ultimately to a fused homogeneous matrix. The dynamic viscoelastic measurements were utilized to continuously monitor the changes of moduli under a controlled heating rate, employing a mechanical spectrometer. Characteristic changes in the viscoelastic behavior were associated with changes in particulate morphology as observed with a scanning electron microscope (SEM). Both viscoelastic and morphological observations were shown to provide details of structural changes in conjunction with the behavior of the PVC-plasticizer interaction, enabling a qualitative discrimination of the gelation and fusion processes. An in situ small-angle light-scattering (SALS) method was performed to make a quantitative estimate for the swollen particles of PVC while they were in the progress of gelation and fusion. From the manner of increase in correlation distances, along with the changes in viscoelastic moduli and morphology, the swelling behavior of the particulate structures were examined on the quantitative basis and brief insight into the complex behavior of the PVC-plasticizer interaction began to be unfolded.