A new and computationally efficient approach is proposed for determining the refractive index of spherical and transparent particles, in addition to their size and 3D position, using digital in-line holography. The method is based on the localization of the maximum intensity position of the photonic jet with respect to the particle center retrieved from the back propagation of recorded holograms. Rigorous electromagnetic calculations and experimental results demonstrate that for liquid-liquid systems and droplets with a radius > 30µm, a refractive index measurement with a resolution inferior to 4 × 10-3 is achievable, revealing a significant potential for the use of this method to investigate multiphase flows. The resolution for solid or liquid particles in gas is expected to be lower but sufficient for the recognition of particle material.