Alkali metals were introduced into heavy main-group iodometallates to get two new IA/IVAheterometallic frameworks [PbI 3 K(pdon)(H 2 O) 2 ] n (1) and {[Pb 3 I 9 K 2 (pdon) 2 (H 3 O)]·H 2 O} n (2) (pdon=1,10-phenanthroline-5,6-dione), which were obtained as single phases by hydrothermal method at different pH values. Compounds 1 and 2 are three-dimensional heterometallic frameworks constructed from the linkage of pdon ligand between iodometallate chains and potassium oxides/iodide clusters. Specially, these two heterometallic frameworks exhibit broadened absorption bands at 700 and 750 nm compared with those of bulk PbI 2 and pdon ligand. The band gap of 2 is wider than that of 1, which is due to the absence of π · · · π interaction in 2. Their thermal stabilities are also discussed.