Crystalline CuSCN films can be obtained by cathodic electrodeposition from solutions containing Cu(II) cation and thiocyanate anion. The change in film structure and morphology due to variation of the deposition conditions is investigated in view of applications of CuSCN in dye-sensitized p-n solar cells. Smaller grain sizes were obtained towards more negative deposition potentials, with higher ethanol fraction in the solvent and in the presence of dye molecules and surfactants as structure-directing additives. The largest effect was seen when varying the anion of the copper(II) salt and the cation of the thiocyanate salt in the deposition bath. While Cu(ClO4)(2) and LiSCN lead to the formation of compact films, plate-like structures are seen with CuCl2 and NH4SCN and rod-like structures with NaSCN. (c) 2007 Elsevier B.V. All rights reserved.