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A theoretical analysis of x‐ray initiation in a high‐pressure discharge using a Boltzmann approach is presented. For a given power of x rays injected in the discharge, we have studied the influence of the x‐ray spectrum on the degradation times of photoelectrons and on the resulting electron distribution function and electron densities. This approach appears to be of interest for the optimization purpose of the initiation of high‐pressure glow discharges.