Artificial membranes formed from amphiphilic block copolymers have shown considerable promise in the field of biomimicry, due to their extended stability, longevity, and ability to reconstitute membrane proteins. The polymeric membranes have been formed in the oil phase utilizing the droplet interface bilayer (DIB) method, an innovative technique that is used to assemble a membranal network of water droplets in oil. This study investigates the DIB formation of polymers in the aqueous phase, as well as the effect of oils on the formation of monolayers. Our study demonstrated that the diblock copolymer PB-PEO could successfully be formed and characterized in the oil hexadecane. DIB formation required application of voltage in order to initiate droplet adhesion, and the removal of voltage caused droplet repulsion, indicating the reversibility of aqueous polymeric DIBs. We also demonstrated the poor solvency of squalene, as the oil is capable of lowering the tension state of polymers in the aqueous phase but were unable to successfully characterize DIBs submerged in squalene. The results of our study show a promising outlook for the application of polymer droplet interface bilayers.