Abstract: The authors describe an electroless deposition method for thin films, based on the irradiation by an x-ray beam emitted by a synchrotron source. Specifically, Ni–P films were deposited at room temperature. This synthesis is a unique combination of photochemical and electrochemical processes. The influence of the pH value on the formation and structural properties of the films was examined by various characterization tools including scanning electron microscopy, x-ray diffraction, and x-ray absorption spectroscopy. Real time monitoring of the deposition process by coherent x-ray microscopy reveals that the formation of hydrogen bubbles leads to a self-catalysis effect without a preexisting catalyst. The mechanisms underlying the deposition process are discussed in details.