The compounds Ba2Bi24Mo10O68 and La2Bi24Mo10O69 were synthesized by the ceramic route and characterized by single crystal and powder X-ray diffraction, respectively. The structure of these phases is isostructural with that of Bi26Mo10O69. Along the b axis columns of [Bi12O14] units are separated by MoO4 tetrahedra and noncolumnar A (A = Ba, La) atoms. UV-visible spectra of Bi26Mo10O69, Ba2Bi24Mo10O68, and La2Bi24Mo10O69 suggest that band gap decreases on substitution of La and Ba for Bi at the noncolumnar site. The photocatalytic degradation of water pollutants such as phenol and substituted phenols was studied. All the catalysts show specificity toward nitro substituent at the para position in the aromatic ring.