Hydrogen fuel cells are a promising energy conversion technology due to its high energy density and zero greenhouse gas emission. As a result, the production of hydrogen from renewable and alternative resources has gained significant interest in recent decades. This paper demonstrates a new approach which uses a pyroelectric energy harvester for water splitting and represents a novel alternative hydrogen source. Pyroelectrics are attractive for harvesting waste heat due to their ability to convert temperature fluctuations into electrical energy. A range of pyroelectric materials and geometries for water electrolysis are analysed to determine, (i) the minimum material thickness to generate a critical potential to initialise water decomposition and, (ii) to maximize the charge and hydrogen mass production. We then successfully demonstrate that an appropriate pyroelectric material, when combined with rectification of the alternating current, can harvest heat fluctuations and generate a sufficient electric potential difference and current for water splitting. By harvesting the pyroelectric electrical energy, a continuous hydrogen bubble production was observed during thermal cycling. Practical routes to maximize the level of hydrogen production for this new concept are also explored. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.