We present a novel and simple method to determine the average composition of multilayers and superlattices by measuring the x‐ray refractive index. Since these modulated structures exhibit Bragg reflections at small angles, by using a triple axis x‐ray spectrometer we have accurately determined the peak shifts due to refraction in GaAs/AlxGa1−xAs and Nb/Ta superlattices. Knowledge of the refractive index provides the average fractional composition of the periodic structure since the refractive index is a superposition of the refractive indices of the atomic constituents. We also present a critical discussion of the method and compare the values of the average fractional composition obtained in this manner to the values obtained from the lattice parameter change in the GaAs/AlxGa1−xAs superlattices due to the Al.