Two new alkali bismuth oxosulfates, [Bi12O15]Li-2(SO4)(4) (I) and [Bi7K2O8]K(SO4)(4) (II), have been synthesized by heating a mixture of Bi2O3, CuSO45H2O, and A(2)CO(3) (A = Li, K), and characterized by single crystal XRD, transmission electron microscopy, and multiphoton SHG and IR spectroscopy. In the above formula the [BixOy] subunits denote the 3D-porous (I) or 1D-columnar (II) polycationic host-lattice formed of edge-sharing OBi4 or O(Bi,K)(4) oxocenterd tetrahedra. The SO42- groups and alkali ions are arranged into channels in the interstices leading to original opened crystal structures for these two first reported alkali oxo-bismuth sulfates. The strong adaptability of the oxocentered framework is demonstrated by the possibility of preparing single crystals of [Bi8.73K0.27O8]K-1.54(PO4)(4) (III) whose crystal structure is similar to those of II with disorder between OBi4 and O(Bi-3,K) tetrahedra and different channel occupancy due to the aliovalent replacement of SO42- for PO43-.