A novel film coating technique, template-assisted electrostatic spray deposition (TAESD), was developed for the synthesis of porous metal oxide films and tested on TiO2. Organic templates are codeposited with the titania precursor by electrostatic spray deposition and then removed during calcination. Resultant films are highly porous with pores casted by uniformly sized templates, which introduced a new level of control over the pore morphology for the ESD method. Employing the amphiphilic block copolymer Pluronie P123, PM MA latex spheres, or a combination of the two, mesoporous, macroporous, and hierarchically porous TiO2 films are obtained. Decoupled from other coating parameters, film thickness can be controlled by deposition time or depositing multiple layers while maintaining the coating's structure and integrity.