Foam-like zinc orthotitanate (Zn₂TiO₄) is successfully synthesized via the wet chemical sol–gel route assisted with a structure-directing diblock copolymer template. The wet chemical route enables spray deposition of Zn₂TiO₄ films. Calcination temperature of the spray-deposited films is shown to be crucial for the synthesis of the compound phase, Zn₂TiO₄. Surface composition and optical properties of the films are also studied. Finally, Zn₂TiO₄ films are shown to offer a reasonable functioning as an electron acceptor in dye-sensitized solar cells, with the best preliminary performance reported so far.