This study is to perform the comprehensive investigation of PVC based ionic plasticized membrane (IPM) production by using room temperature ionic liquid (RTIL)‐based additives and the membrane application of selective Cr(VI) removal. Some significant parameters related to membrane structures that are membrane thickness, plasticizer rate, and type, RTILs rate, and type, the average molecular weight of PVC were studied to define the excellent polymeric membrane film composition. After that, the PVC based polymeric film used in the Cr(VI) transport and initial mass transfer coefficient (Jo) were about 3.57 × 10−7 mol s−1 m−2 by decyl substituted RTIL as an additive. Also, optimized membrane transport process has been considered as selective enough for Cr(VI) in the presence of the other heavy metal ions. Surface characterizations of the membranes have been performed to clarify the structural and the morphological assessment of IPMs at initial and end of Cr(VI) transport by SEM‐EDX, AFM, contact angle measurement and found a good relationship between the molecular structure of RTIL additive and membrane morphology. As we know that lots of researchers are still trying to find environmentally friendly, inexpensive and straightforward processes to remove toxic substances from industrial effluents or natural sources. At that point, our results can open a gate for cheap, novel and environmentally friendly Cr(VI) removal by PVC based membrane. J. VINYL ADDIT. TECHNOL., 25:E107–E119, 2019. © 2018 Society of Plastics Engineers