Using a multifunction spectrophotometer, the refractive index of a pigment can be estimated by measuring the backscattering of light from the pigment in immersion liquids having slightly different refractive indices. A simple theoretical Gaussian function model related to the optical path distribution is introduced that makes it possible to describe quantitatively the backscattering signal from transparent pigments using a set of only a few immersion liquids. With the aid of the data fitting by a Gaussian function, the measurement time of the refractive index of the pigment can be reduced. The backscattering measurement technique is suggested to be useful in industrial measurement environments of pigments.