Hyper-Rayleigh scattering (HRS) or incoherent second-order light scattering technique has been used to investigate the second-order optical nonlinearities of nanoparticles and seems sensitive to nanoparticle aggregation. In the present work, CdS and ZnS nanoparticle colloids are prepared by the method of colloidal chemistry. From absorption spectra their average diameters are determined to be 5.0 nm for CdS and 2.5 nm for ZnS. Composite CdS-ZnS colloids are obtained by mixing the two colloids at different concentration ratio. The formation of the composites is confirmed by fluorescence measurement. The reduction of emission intensity of the ZnS colloid at 428 nm is observed with increasing CdS concentration, due to fluorescence quenching of the ZnS colloid after forming CdS-ZnS composites. The apparent combining constant of the two nanoparticles is determined to be 8.1×104 mol−1.L by fitting the relative fluorescence intensity of F
0/F vs. the added CdS concentration. Upon 1064 nm laser pulse excitation, HRS signal is determined at frequency-doubling wavelength (532 nm) using photomultiplier tube (PMT). HRS experiments show that the composite CdS-ZnS colloids exhibit stronger HRS signal than both CdS and ZnS colloids, and a maximum of HRS signal appears at concentration ratio of [CdS]/[ZnS]=1. This is attributed to that the composite CdS-ZnS nanoparticles have lower symmetry which contributes substantially to the second-order optical nonlinearity of nanoparticles in the electric dipole approximation.