Two new photoluminescent magnesium-based coordination polymers, Mg(int)(2)·H(2)O (1) and Mg(nt)(2) (2), were synthesized under solvothermal conditions. Structural analyses reveal that they have different 3,6-connected frameworks with rutile- and anatase-type topologies, respectively. Compound 1 remains stable after the removal of its guest molecules and it exhibits weak ferroelectric behavior.