Benzo[a]pyrene is a carcinogen often present in diesel. For pervaporative removal of benzo[a]pyrene from n-tetradecane, representing a model diesel composition, both conventional as well as statistically designed experimental methods have been carried out. The effect of membrane composition, thickness, the effect of membrane pretreatment time and operating temperature on pervaporative separation have been investigated by response surface methodology, RSM for efficient permeation of target compound. The suitable membrane has been further used to study the effect of different physico-chemical parameters on permeation conventionally. RSM has also been applied to optimize the operational conditions of pervaporation process to maximize the response, i.e., the pervaporation separation index. With the design of experiments, the quadratic response surface models have been developed to link the response with input variables via mathematical relationships. The maximum value of Pervaporation Separation Index obtained is 1.9654 kg m−2 h−1. The optimized process condition’s run time is 10.79 h, the feed PAH concentration is 166.34 ppm with a permeate side pressure of 0.73 mmHg and an operating temperature of 451.25 K. © 2018, Institute of Chemistry, Slovak Academy of Sciences.