Abstract Porous polymer films show interesting properties as ion selective membranes. In this work, poly(1,2-diaminobenzene) and polytyramine were deposited from hexagonal liquid crystal templates using two different surfactants. Resulting films were investigated to find evidence of mesoporous structures. While templated poly(1,2-diaminobenzene) has already been described as charge selective in the past, electrochemical experiments in this work demonstrate that another mechanism (most likely, size selectivity) also contributes to its ion selective behaviour. Films were characterised using spectroscopic ellipsometry and impedance spectroscopy. Results provide further evidence for the porosity, thinness, and the presence of ions in the templated poly(1,2-diaminobenzene) films. It is demonstrated that the use of a low-cost surfactant (Brij 56) is sufficient for the templating process. In contrast, polytyramine gave no evidence of being templated by the liquid crystal.