Porous pillared materials have been synthesized from substituted tri-and tetratitanates (Na2Ti3-xMxO7, K2Ti4-xMxO9, M = Mn, Fe, Co, Ni, Cu, x less than or equal to 0.3) by a stepwise exchange process. The microstructure of pillared samples was characterized by a number of cleavages running parallel with TiO6 layers, which produced a waffle-like texture. The pillared samples showed 10-25 times larger BET surface areas (50-120 m(2)/g) as compared to pristine samples. The photocatalytic activity of 1 wt.% Pt/titanates for H-2 evolution from CH3OH/H2O mixtures was enhanced by pillaring in accord with an increase of the surface area. Partial substitution of various transition elements for the Ti site significantly affected the H-2 evolution rate.