Hydrothermal reactions of lanthanide oxide, lead chloride, I(2)O(5), and H(2)O at 200 degrees C led to four novel quaternary compounds, namely, Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = La-Nd). They are isostructural, and their structures feature a complicated 3D network composed of LaO(9) and PbO(6) polyhedra interconnected by asymmetric IO(3) groups. Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = La, Pr, Nd) display moderate second harmonic generation efficiencies of about 2.0, 1.0, and 0.8 times the value of KH(2)PO(4), respectively. These compounds are thermally stable up to 520 degrees C. Luminescence measurements indicate that Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = Ce, Pr, Nd) exhibit strong emission bands in the visible or near IR region. Magnetic studies indicate that there exist significant antiferromagnetic interactions between magnetic centers in Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = Pr, Nd).