Chemical and physical synthesis routes were combined to prepare macroporous CaCu3Ti4O12 thin films by pulsed laser deposition onto poly(methyl methacrylate) (PMMA) microsphere templated substrates. These films showed remarkably enhanced gas sensitivity compared with control films deposited on untreated substrates, demonstrating the virtues of combining thin film physical vapor deposition (PVD) techniques in concert with colloidal templates to produce macroporous structures of inorganic films with enhanced surface activity for applications in chemical sensors, catalysts, and fuel cells.