The two novel organic hybrid iodoplumbates [Hhbpt]2[H2hbpt][H4hbpt][Pb5I18]·9H2O (1, hbpt = 1H-3,5- bis(pyrazinyl)-1,2,4-triazole) and [Pb2I(bpt)2(H2O)3(I3·1/2I2)] (2) were synthesized under hydrothermal conditions. 1 contains a new type of pentanuclear cluster [Pb5I18]8- anion, while 2 comprises an unprecedented 2-D polyiodoplumbate layer. Both 1 and 2 are potential semiconductors with narrow absorption edges of 1.98 eV for 1 and 1.38 eV for 2. 2 also shows photocurrent response and photoluminescent properties.