The pervaporation separation and the swelling behavior of chlorinated hydrocarbon/acetone mixtures were investigated using natural rubber (NR) and epoxidized natural rubber (ENR) membrane with 25 and 50 mol% epoxidation, respectively. The swelling degree increases with increase in the epoxidation level. The flux and separation factor of the membranes were determined both as a function of mole percent epoxidation and of the feed mixture composition. The membranes were found to be permselective to chlorinated hydrocarbons from acetone-chlorinated hydrocarbon mixtures. The Aux decreases with increase in epoxidation level, whereas the separation factor increases. The permeation decreases and separation factor increases with increase in the acetone feed concentration. The availability of raw materials, low cost of implementation and easy processability of the system makes this method of separation highly applicable and recommendable.