The hybrid sulphur process is one of the most promising thermochemical water splitting cycles for large scale hydrogen production. While the process includes an electrolysis step, the use of sulphur dioxide in the electrolyser significantly reduces the electrical demand compared to conventional alkaline electrolysis. Solar operation of the cycle with zero emissions is possible if the electricity for the electrolyser and the high temperature thermal energy to complete the cycle are provided by solar technologies. This paper explores the possible use of photovoltaics (PV) to supply the electrical demand and examines a number of configurations. Production costs are determined for several scenarios and compared with base cases using conventional technologies. The hybrid sulphur cycle has promise in the medium term as a viable zero carbon production process if PV power is used to supply the electrolyser. However, the viability of this process is dependent on a market for hydrogen and a significant reduction in PV costs to around $1/W(p). Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.