TiO2 supported layered compounds (SLCs) with different loading amounts of layered compound (LC) were prepared via impregnating TiO2 with a KOH solution and then calcining at high temperature. The photo-reduction of Cr(VI) catalyzed by SLCs and LC was also examined. Results showed that LCs were observed in the surface of SLCs and they were generated by a solid-phase reaction between KOH/K2CO3 and TiO2 at high temperature. At a solution pH of 1.0, the Cr(VI) photo-reduction showed 1/2 order kinetics in the presence or absence of TiO2. However, the Cr(VI) photo-reduction catalyzed by LC fitted zero order kinetics. In the presence of SLC with low loading amount of LC, the Cr(VI) photo-reduction showed the same kinetics as that over TiO2. In contrast, the kinetics of Cr(VI) photo-reduction catalyzed by SLC with high loading amount of LC was similar to that by the unsupported LC. SLC with a certain loading amount of LC exhibited enhanced catalytic activity for Cr(VI) photo-reduction. The enhanced catalytic activity was related to the electron transfer between the support and the LC.