Optimal operation of the pervaporation process for the removal of multicomponent VOCs from water was studied. The data obtained were for the treatment of wastewater containing toluene, trichloroethane (TCE), and methylene chloride using poly(dimethylsiloxane) (PDMS) membrane in the form of a hollow fiber membrane module. In this study, the influence of process variables (feed composition, Reynolds number, flow rate, membrane thickness, and downstream pressure) on the module performance and process economics was studied. A population-based tool was used to optimize the process variables, and a real coded genetic algorithm was used to determine the optimum process conditions for the minimum annual wastewater treatment cost for a fixed toluene removal fraction without recycling of the permeate. It was found that the treatment cost for a multicomponent system is less than that of a single-component system at the global optimum of the process variables.