A new series of solid solutions of the type, A(x)Ba(1-x)Bi(2)Mo(4)O(16) (A = Ca, Sr, Pb) have been isolated. The domain of the solid solutions is very narrow and is in the range (0.01 <= x <= 0.10). All the phases were synthesized by the solid-state technique. The crystal structure is similar to that of the monoclinic scheelite type BaBi2Mo4O16. The structure consists of layers of [Bi2O2] units separated by (Ba/AO)(10) units and isolated MoO4 tetrahedra. Their semiconductor band gaps render them as potential materials for photocatalysis. (c) 2007 Elsevier Ltd. All rights reserved.