Lead(II) coordination polymer [Pb(5,5 0 -dmbpy) (l-NO 3 ) 2 ] n (1) and mononuclear complex [Pb(6,6 0 -dmbpy) (NO 3 ) 2 ] (2) (where 5,5 0 -dmbpy is 5,5 0 -dimethyl-2,2 0 -bipyridine and 6,6 0 -dmbpy is 6,6 0 -dimethyl-2,2 0 -bipyridine) were synthesized from reaction of lead(II) nitrate with 5,5 0 -dmbpy and 6,6 0 -dmbpy, respectively. Both complexes were thoroughly characterized by elemental analysis, infrared, 1 H and 13 C NMR, UV-Vis, emission spectroscopy, as well as single-crystal X-ray diffraction. Polymer 1 possesses one-dimensional (1D) chain structure, whilst complex 2 exhibits a discrete complex which provide an extended chain parallel to the [001] direction, via weak intermolecular C-HÁÁÁO hydrogen bonding. Coordination number of Pb 2? in 1 and 2 are 8 and 6, respectively, with the stereochemically active lone pair, resulting in the hemidirected geometry for both complexes. The nitrate anions exhibit a tridentate chelating/bridging mode in 1, and a bi-chelating mode in 2. The supramolecular features in these complexes are guided/influenced by weak directional intermolecular C-HÁÁÁO hydrogen bonding (1 and 2) together with p-p and C-HÁÁÁp (1) interactions. The luminescence studies of 1 and 2 confirmed that the position of methyl substituent on 2,2 0 -bipyridine rings has a profound effect on the fluorescence emissions.