Single crystals of (TBA)(2)[Cd(dmit)(2)] (TBA=bis-tetrabutylammonium) were prepared and characterized by elemental analyses, proton nuclear magnetic resonance ((HNMR)-H-1), infrared (IR) and Raman spectra, X-ray powder diffraction spectroscopy and UV-vis-NIR absorption spectrum. Thermal analyses show that (TBA)(2)[Cd(dmit)(2)] possesses high thermal stability. The third-order nonlinear optical properties of the crystal in acetonitrile solution were investigated using the laser Z-scan technique with 20 ps pulses at 532 nm. A typical centro-symmetric profile was observed, which indicates no nonlinear absorption. The magnitudes of third-order nonlinear refraction index n(2) and the second order molecular hyperpolarizability gamma were 9.409 x 10(-18) m(2)/W and 2.774 x 10(-30) esu, respectively, which reveal that the crystal is a potential candidate for application as all-optical switching devices at blue-green light band. (C) 2012 Elsevier B.V. All rights reserved.