Tin (II) sulfide (SnS) is a promising semiconductor material for next-generation solar energy conversion due to its favorable bandgap, elemental abundance, low toxicity, and low cost. A major challenge, however, lie in the low open circuit voltages that are typically obtained in SnS-based devices. Herein, a low-cost solution-phase deposition technique is used to prepare SnS thin films and investigate different junction materials (Ga2O3 and In2S3) to improve the photovoltage in SnS-based water splitting photocathodes. Molecular inks are prepared by dissolving SnS powder in solvent mixtures of ethylenediamine and 1,2-ethanedithiol. SnS thin films are then successfully deposited by spin coating the inks onto substrates, followed by a heat treatment at 350°C in an inert atmosphere. With a photoelectrode based on a SnS/Ga2O3 heterojunction, an onset potential of +0.25 V versus reversible hydrogen electrode (RHE) is achieved for photoelectrochemical hydrogen evolution in pH 7 phosphate buffer, which is until now the earliest onset potential (highest photovoltage) among nontoxic replacements to CdS junctions in SnS-based water splitting systems.