There has been a steady increase in utilizing nanoporous materials across a wide variety of fields leading to an increased demand for more economical and superior materials. The present work contributes towards addressing these concerns by using commercially and easily available chemicals to synthesize electrostatically self-assembled amphiplexes. These amphiplexes have been prepared by combining polyelectrolyte-surfactant complexes with co-surfactant and oil and they show long range order at the nanoscale exhibiting various morphologies such as cubic, lamellar and hexagonal. Employing small angle x-ray scattering, phase transitions and swelling behavior were investigated in these amphiplexes as a function of ionic strength, co-surfactant concentration and oil concentration. With the endeavor to capture the nanostructured order demonstrated by these amphiplexes onto a solid polymeric material, the oil phase was polymerized. The polymerization was optimized by two methods. First, the polymerization was successfully delayed using a catalyst poison and second, the catalyst loading was optimized. Upon polymerization, phase transition and swelling behavior studies of amphiplexes revealed no significant influence of ionic strength, co-surfactant concentration and oil concentration on polymerized amphiplexes. A phase separation is observed with the amphiplexes exhibiting a conserved hexagonal phase upon polymerization.