The composition of Ba(0.785)Bio(0.127)Y(0.017)TiO(3) (BaBiYTiO) belongs to the BaTiO3-Bi2O3-Y2O3 system. A dielectric study on ceramics performed at temperatures in the range (77 K-500 K) and frequency (10(2)-2 x 10(5) Hz) revealed ferroelectric relaxor behaviour with a phase transition close to room temperature. The conductivity of BaBiYTiO obeys to an Arrhenius-type law with activation energy equals to 0.21 eV, in conformity with a small polaron hopping where most electrons are localized. The oxide is lightly doped leading to a wide space charge region (480 nm) in which photoeffect occurs. The presence of domains promotes the separation of the charge carriers through conversion of light into chemical energy. The electrode acquired n-type behaviour, evidenced from the negative thermopower and anodic photocurrent. The flat band potential V-fb (-0.46 V-SCE) and the electron density N-D (2.82 x 10(15) cm(-3)) were determined in KOH solutions (0.5 M). The Nyquist plot exhibits two well defined time constants characteristic of bulk and grains boundaries contributions and an equivalent electrical circuit has been proposed according to the Randles model. The energy band diagram shows the potentiality of the oxide for the solar-energy conversion. BaBiYTiO has been tested successfully for H-2 production upon visible light when combined to the delafossite CuFeO2 as sensitizer. An evolution rate of 24 mu mol mn(-1) and a quantum yield of 0.4% under polychromatic light were obtained. (C) 2010 Elsevier Ltd. All rights reserved.