A novel and environmentally-friendly procedure for the preparation of polymer inclusion membranes (PIMs) containing an ionic liquid is presented for the first time. Traditionally, PIMs are prepared by a solvent casting method with the use of harmful organic solvents. Here we report a new solvent-free procedure based on a thermal-compression technique which involve the melting of the components of the PIM and the application of a high pressure to the melted specimen to form a flat-sheet film. In our study, we have tested different polymers, such as two cellulose derivatives as well as two thermoplastic polymers, polyurethane (TPU) and poli ε-caprolactone (PCL). The ionic liquid (IL) trioctylmethylammonium chloride (Aliquat 336) has been used to produce PIMs with a fixed composition of 70% polymer-30% IL (/). Both TPU and PCL polymers provide successful membranes, which have been thoroughly characterized. PIMs based on the polymer PCL showed a high stability. To test whether the properties of the IL were affected by the preparation conditions, the extraction ability of Aliquat 336 was investigated for both PCL and TPU membranes in terms of Cr(VI) extraction. Satisfactory values (90% extraction) were obtained for both membranes tested, showing this novel procedure as a green alternative for the preparation of PIMs with ILs.