This paper presents a non-invasive measurement method for simultaneous characterization of diameter and refractive index of transparent fibres. The method is based on scattering of a polychromatic beam of light by a side-illuminated fibre under study. Both quantities of interest are inversely calculated from the scattering far-field region in the vicinity of the primary rainbow. The results of practical measurements are examined with the use of a novel optical system for laboratory-level tests. An analysis of prediction errors for 20– 120 μm thick fibres having various refractive indices helps to assess the outcome of the measurement data. The results show a clear route to improve the measurement process in on-line industrial process control.