We present a robust, precise, and accurate method to simultaneously measure the refractive indices of two transparent materials within an interference coating. This is achieved by measuring both a photometrically accurate transmittance spectrum and the as-grown individual layer thicknesses of a thin-film multilayer structure. These measurements are used for a TMM-based curve-fitting routine which extracts the refractive indices and their measurement uncertainties via a Monte-Carlo-type error propagation. We demonstrate the performance of this approach by experimentally measuring the refractive indices of both, GaAs and Al 0.929 Ga 0.071 As, as present in an epitaxial distributed Bragg reflector. A variety of devices can be used to obtain the transmittance spectrum (e.g., FTIR, grating-based spectrophotometer) and layer thicknesses (e.g., SEM, TEM, AFM), the discussed approach is readily adaptable to virtually any wavelength region and many transparent material combinations of interest. The subsequent model-fitting approach yields refractive index values with 10 −4 -level uncertainty for both materials.