The perovskite Ba1-xEu2x/3(Ti0.75Zr0.25)O-3 (x = 0.025, 0.05) have been prepared by solid state reaction. A dielectric study on ceramics performed in the ranges of temperature (77-500 K) and frequency (10(2)-2 x 10(5) Hz) reveal typical relaxor behavior and diffuse phase transition. The relaxor parameters (T-m, Delta T-m, Delta epsilon(r)'/epsilon(r)') decrease slightly with the increase of Eu-dopant concentration. The dielectric relaxation rate follows the Vogel-Fulcher relation with activation energy of 21 meV, an attempt frequency f(o) = 1.1 x 10(8) Hz and a static freezing temperature T-f = 95 K for x = 0.025. An optical gap of 2.25 eV is obtained from the diffuse reflectance spectrum. The photo-electrochemistry throws light on the nature of the electronic bands. The Mott-Schottky plot is characteristic of n-type conduction from which a fiat band potential of -0.60 V-SCE and an electrons density of 1.2 x 10(18) cm(-3) are determined for the composition x = 0.025. The upper valence band located at 6.4 eV below vacuum is made up of O2-: 2p orbital whereas the conduction band consists of empty 3d levels (4.13 eV) with a high reducing ability. The energetic diagram clearly assesses the photoactivity of the perovskite. The performance is improved when the crystallite size becomes comparable with the length of the nanodomains. As application, 95% of chromate (10(-4) M) is reduced after 6 h of exposition to sunlight (AM1). (C) 2013 Elsevier Ltd. All rights reserved.