By combination of the large organic cation [trans-4-(4-dimethylanilino-styryl)-N-methyl-pyridinium with nanocluster anions ([Cd4(SC6H5)10]2- for compound 1 and [Cd4(SC6H5)6I4]2- for compound 2), two new hybrids were obtained and the structure of the [Cd4(SC6H5)6I4]2- cluster was first characterized by single-crystal X-ray diffraction. A novel supramolecular dimer [Cd4(SC6H5)10]2-2, connected via strong ð-ð interactions, was observed in 1, whereas every two [Cd4(SC6H5)6I4]2- clusters in 2 were linked by multiple C-HâââI hydrogen bonds forming dimers, which, as building blocks, were further connected to each other via C-HâââI hydrogen bonds and weak IâââI interactions to form novel 1D helical chains. The UV-visible-near-IR spectra, one-photon excited photoluminescence, and two-photon pumped lasing were measured. The organic chromophore exhibits enhanced PL and two-photon pumped lasing in the two hybrids.