In this study, we investigated the influence of TiO2 content and thickness of polystyrene (PS) template on film‐formation behavior of PS/TiO2 composites using fluorescence and ultraviolet–visible techniques in conjunction with scanning electron microscopy. Films were prepared by coating PS templates with various layers of TiO2 using dip‐coating method. The results showed that PS latexes present complete film formation on top surface of composites. After extraction of PS, a well‐defined interconnected porosity were obtained for thin films when TiO2 content was increased, whereas thick samples did not present any interconnected porous structures above a certain TiO2 layer. POLYM. ENG. SCI., 54:288–302, 2014. © 2013 Society of Plastics Engineers