Bulk LaVO3 (LVO) is known to provide an optical bandgap of 1.1 eV which is interesting for photovoltaic applications. Here, we compare the properties of LVO thin films using different techniques, namely pulsed laser deposition, spin coating by solgel and sputtering. ZnO/LVO p-n junctions were fabricated in order to obtain solar cell architectures. The grown films were analyzed with Surface photovoltage and Scanning Kelvin Probe Microscopy. The analysis of the junctions showed that the photogenerated electron-hole pairs are poorly separated and therefore not efficiently collected. LVO has shown the particularity to provide very high work function (4.6 eV) and a great dependence of the electrical and optical properties on the growth conditions, including the oxygen stoichiometry and the La/V ratio of the films.