We synthesized Sb2S3 by a simple sulfurization of Sb metal prepared by electrodeposition at relatively low temperatures and demonstrated the use of a TiO2 buffer/protection layer for water splitting applications, yielding photocurrent densities of 3 mA cm -2 at 0 V vs RHE and ~ 9 mA cm - 2 at more negative bias). However, the photovoltage as estimated from the onset potential was low (~ 0.1 V). From XPS band alignment studies and bias dependent IPCE measurements, the low photovoltage was attributed to a large conduction band offset of 0.7 eV and unfavorable band bending at the heterointerface. The photovoltage was improved by employing a buffer layer (In2S3) with a higher lying conduction band position, thus reducing the conduction band offset and giving an earlier onset potential (~ 0.25 V photovoltage). This work also demonstrates that In2S3 is a promising junction material for Sb2S3. Further improvements in controlling the doping (making ptype Sb2S3 for downward conduction band bending at the junction) and band alignment of Sb2S3 (buffer layers with conduction band position nearer to that of Sb2S3) will make it increasingly attractive for cost-effective large-scale water splitting.