Natural rubber (NR) membranes crosslinked by four different systems viz., conventional (CV), efficient (EV), dicumyl peroxide (DCP), and a mixture consisting of sulfur and peroxide (mixed), were employed for the separation of n-hexane/acetone mixtures of different compositions. The membranes exhibited preferential permeation toward n-hexane because of the closer solubility parameter values. The selectivity of the membranes depended on the nature and distribution of crosslinks between the macromolecular chains of the membrane but was independent on the thickness of the membrane. The effects of feed composition, cure time of the membranes, and the molecular size of the permeate on the permeation flux and selectivity were investigated.