Visible-light responsive TiO2 photocatalyst modified by catechol-type interfacial surface complexes (ISC) was designed by the reaction of Ti-OH moieties with catechol and such derivatives as 3-methoxycatechol involving electron-donating groups (EDG) and 3,4-dihydroxybenzonitrile involving electron-withdrawing groups (EWG). The visible-light response of the ISC is attributed to excitation from the donor levels created in the TiO2 midband. The phenyl-ring-substituted groups strongly influence the electronic structures of the ISC: the catechols with substituted EWG induce an anodic shift of the donor levels accompanied by an enlargement of the energy gaps, compared with catechol without substituted groups. The photocatalytic activities for H-2 evolution from triethanolamine aqueous solutions were systematically investigated. It was confirmed that the more anodic the oxidative potentials of photoinduced holes in the ISC are, the higher the photocatalytic activities they exhibit. (C) 2015 Elsevier Inc. All rights reserved.