The solvothermal reaction of PbI2, KI and HI in a H2O/DMF mixed solution in the presence of the coordination functional template hexamethylenetetramine (hmta) produced a 2-D iodoplumbate hybrid [Hhmta]2[(hmta)2Pb4I10]·2DMF·H2O (1). The hmta molecule was methylated by MeOH to form a mhmta+ (mhmta+ = N-methylhexamethylenetetramine) cation in the same reaction in H2O/MeOH solution. The mhmta+ cation lost its coordination function, leading to the formation of the 2-D iodoplumbate hybrid [mhmta]4[Pb3I10]·H2O (2). In 1, the PbI5 units are interconnected via edge- and face-sharing into a 1-D chain [Pb4I10]n2n−. The [Pb4I10]n2n− chains are linked by μ-hmta bridging ligand to form a 2-D [(hmta)2Pb4I10]n2n− layer. In 2, three PbI6 octahedra are joined by face-sharing to form a trinuclear [Pb3I12] SBU. The [Pb3I12] SBUs are connected into a 2-D [Pb3I10]n4n− anionic layer by corner- sharing. Compounds 1 and 2 exhibited rapid photocurrent responses with steady current densities of 7.71 μA·cm−2 and 10.68 μA·cm−2, respectively. These compounds exhibited high catalytic activity in the photodegradation of crystal violet with degradation rates of 96.5 % over 1 and 97.8 % over 2.