SERS spectra of bilirubin and its complexes were determined in Ag sol by the technique of the connection between NIR-FT-Raman and SERS. The spectra showed that this kind of biological complexes, which is closely related to gallstones, differ in coordination pattens and adsorptive orientation as well. The reason why the black-pigment gallstone exhibits that peculiar dark color was also given from the coordination-chemistry point of view.