A series of novel complexes bearing high fluorescence quantum yields and showing the peak two-photon absorption (2 PA) cross-sections in the near-infrared region, Zn(SCN) 2 L 2 (1), [Cd(SCN) 2 L 2 ] n (2), Co(SCN) 2 L 4 (3), Ni(SCN) 2 L 4 (4), [CdHgL 2 (SCN) 4 ] n (5) and [MnHg(SCN) 4 L 2 ] n (6), containing functional chromophore (L=(E)-(4-diethyl anilinostyryl)pyridine), were synthesized in high yields. Crystal structures of all the complexes were confirmed. Hetero-metal complexes (5, 6: L:M = 1:1) present much higher two-photon absorption (2 PA) cross-sections (σ) in comparison with those of the homo-metal complexes (L:M = 4:1 in 3 and 4, L:M = 2:1 in 1 and 2) and the free ligand (L) which may due to the fact that the hetero-metal complexes have more bridged anions (SCN − ), conjugated subunits –[Hg(SCN) 2 M]– and –[Hg 2 (SCN) 4 M 2 ]–. In addition, the results revealed that 2 PA response was much enhanced for the Zn(SCN) 2 L 2 and two-photon fluorescence cell imaging experiment proved its potential application.