The principle of the optical technique critical angle refractometry, used to determine the size and refractive index of spherical particles (with relative refractive index below unity) in liquid flows, was investigated. This technique is based on the observation of the particle scattering pattern around the critical angle. Similarly to the recent technique developed for rainbow scattering pattern analysis for droplet temperature and size measurements, it is shown that the relative particle refractive index (m(r) < 1) and size can be determined from the position of the primary diffraction fringe and from the angular spacing between two fringes. Explicit equations for refractive index and particle size measurement were derived from the first-order term of the physical optics approximation. An experimental validation test and numerical computations based on the Lorenz-Mie theory were used to validate the principle of the proposed technique and to estimate its sensitivity, which was shown to be of the same order as that of the rainbow technique. This technique is considered to be useful for various applications in liquid multiphase flows where the particles size and material are to be characterized.