By combination of the large organic cation [trans-4-(4-dimethylanilino-styryl)-N-methyl-pyridinium with nanocluster anions ([Cd-4(SC6H5)(10)](2-) for compound 1 and [Cd-4(SC6H5)(6)I-4](2-) for compound 2), two new hybrids were obtained and the structure of the [Cd-4(SC6H5)(6)I-4](2-) cluster was first characterized by single-crystal X-ray diffraction. A novel supramoleculax dimer {[Cd-4(SC6H5)(10)](2-)}(2), connected via strong.7r-,7 interactions, was observed in 1, whereas every two [Cd-4(SC6H5)(6)I-4](2-) clusters in 2 were linked by multiple C-H center dot center dot center dot I hydrogen bonds forming dimers, which, as building blocks, were further connected to each other via C-H center dot center dot center dot I hydrogen bonds and weak I center dot center dot center dot I interactions to form ovel 1D helical chains. The LTV-visible-near-IR spectra, one-photon excited photoluminescence, and two-photon pumped lasing were measured. The organic chromophoreexhibits enhanced PL and two-photon pumped lasing in the two hybrids.