Polyvinylchloride (PVC) was mechanochemically modified (mmPVC) by a ball mill. The dynamic rheological properties of PVC and mmPVC dope solution [containing PVC/ N , N -dimethyl acetamide (DMAc)/polyethylene glycol 400 (PEG 400)/polyethylene glycol 6000 (PEG 6000)] were studied with the advanced rheometric expansion system of AR1000 at different temperatures (40, 60, and 80 °C). PVC and mmPVC membranes were prepared at different dope solution temperatures (50 and 80 °C), and the structure and permeation of membranes were analyzed. It was showed that homogeneous degree of PVC dope solution deteriorated as temperature increased; while homogeneous degree of mmPVC dope solution improved at 80 °C. Mechanochemical modification led to the forging of hydroxyl group into PVC molecular chains, and the storage modulus ( G ′) of modified PVC dope solution increased. The gel point of mmPVC dope solution occurred at 77.3 °C, and the viscosity ( η ) increased significantly. As the dope solution temperature increased, the permeation of PVC membrane increased from 158.8 to 236.7 L/(m 2 h); while the permeation of mmPVC membrane decreased from 349.2 to 302.3 L/(m 2 h).