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We present an in-situ energy dispersive X-ray fluorescence measurement of the content of Chromium and Nickel in the fumes produced by selective laser melting on an Inconel 625 powder. Significant variations of the intensities of the Chromium and Nickel Kα fluorescence lines were evidenced as a function of the laser power, lasing velocity and chamber atmosphere. Calibration has been carried out using Monte–Carlo particle transport simulations allowed to obtain a quantitative estimate of the Chromium and Nickel mass fraction in the fumes. The experimental data has been compared to the predictions of an analytical physico-chemical model with consistent results. This approach thus also allows to provide information on the temperature of the metallic bath.