This paper presents a new photoelectrochemical (PEC) H-2 production system which is capable of providing clean energy and water, and multi-generation of H-2, electricity, heat and industrial chemicals from a single clean, abundant and renewable source: sun. This novel system maximizes solar spectrum utilization and increases system efficiencies by generating more outputs from solar energy alone. The hybrid PEC-chloralkali system, coupled with PV/T (Photovoltaic Thermal), is capable of producing H-2, Cl-2, electricity, and heat simultaneously. Incoming solar light is split into high-energy photons (with wavelengths lower than 400 nm) and low-energy photons. The high-energy portion is used to generate photocurrent in the reactor, and the remaining part is sent to the PV/T. This PV/T supports the electricity needs of the system and also provides electricity output for the end user. Moreover, the heat recovered from PV/T is a system output. The findings suggest that this system is capable of producing H-2 and Cl-2 as well as heat and electricity with higher efficiencies than the reported PV electrolysis and PEC-based H-2 production efficiencies in the literature. (C) 2016 Elsevier B.V. All rights reserved.