A new series of hybrid dyes, trans-4-(4'-N,N-dialkylaminostyryl)-N-methyl pyridinium [Cd(SCN)(3)(-)](n) [alkyl Me(1), Et(2), Pr(3) and n Bu(4)] have been successfully synthesized from hybrids of inorganicpolymers and organic chromophores. The structures of four new hybrid dyes were characterized by single-crystal X-ray diffraction first. The particular features of the hybrid dyes are (1) the inorganicanions form isolated polymeric one-dimensional zig-zag chains of [Cd(SCN)(3)(-)](n) with an extended pi-conjugation system within the polymeric -[M-S-C N]-M center dot center dot center dot chain and high polarizabilities; and (2) the organic cationic chromophores determine their optical properties. Experimental results revealed that the TPA cross-section values and overall energy conversion efficiencies of hybrid dyes with different alkyl pendant groups have obviously increased from 1 to 4, and in particular, have been substantially enhanced compared to their corresponding iodide analogues 1'-4'. Therefore, we speculate that such increases are attributable to arrangements ofinfinite anionic [Cd(SCN)(3)(-)](n) chains and synergic effects with chromophore cations.