Investigations of inorganic oligomers are important in both chemistry and physiology. In this contribution, we propose a laser induced light scattering imaging (LSI) and a total internal reflected light scattering imaging (TIR-LSI) technique, and apply them to characterize the interactions of inorganic oligomers with biopolymer in aqueous phase and at liquid/liquid interface, respectively. In aqueous medium, synthetic chromium(III) hydrolytic oligomers (CrHO) react with DNA, and the resultant binary could be extracted into the H 2 O/CCl 4 interface in the presence of triocyctyl phosphine oxide (TOPO), forming a DNA–CrHO–TOPO ternary amphipathic complex at the interface with the associate constant of 1.32×10 3 mol −1 dm 4 for a given 1.0×10 −4 moll −1 TOPO. Under the excitation of a 441-nm He–Cd laser light beam, the resultant light scattering and total internal reflected light scattering (TIR-LS) signals of the formed binary in aqueous phase and ternary at liquid/liquid interface could be easily captured using a common microscope coupled with a CCD camera. By digitally analyzing the CCD captures, we demonstrate that aggregations of the CrHO–DNA binary in aqueous phase and DNA–CrHO–TOPO ternary at liquid/liquid interface have occurred, respectively.