The photocatalytic activities of triple-layered Aurivillius phases, Bi(2)A'NaNb3O12 (A'= Sr, Ca) and Bi2CaNaTa3O12, and of protonated forms prepared from these Aurivillius phases through selective leaching of bismuth oxide sheets were investigated. UV-Vis diffuse reflectance spectra showed blue shifts of the adsorption edges upon selective leaching. Although none of the triple-layered Aurivillius phases were active for photocatalytic H-2 evolution from a 20 vol% ethanol solution, all the corresponding protonated forms showed photocatalytic activities for H-2 evolution. The effects of the changes in electronic structures and interlayer surface creation on photocatalytic activities are discussed. (C) 2004 Elsevier B.V. All rights reserved.