Pervaporation process is a membrane based separation process. Polymer membranes were widely used for separating liquid mixtures using pervaporation process. In this study, composite membranes were prepared by mixing natural graphite (NG) and silicone rubber (QM) using two roll mill. Synthesized composite membrane was used for the separation process. The composite membrane reveals the impressive separation performance of methanol-toluene mixtures with preferential selectivity towards methanol. 10 phr (parts per hundred) natural graphite filled membrane obtained best flux and 15 phr membrane showed better selectivity. Optimal separation performance with the permeation flux of 386% and separation factor 1.5 times compared to QM control membrane is obtained. The study confirmed that increasing toluene feed concentration improved the selectivity of membranes.