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Critical phenomena in complex networks, and the emergence of dynamical abrupt transitions in the macroscopic state of the system are currently a subject of the outmost interest. We report evidence of an explosive phase synchronization in networks of chaotic units. Namely, by means of both extensive simulations of networks made up of chaotic units, and validation with an experiment of electronic circuits in a star configuration, we demonstrate the existence of a first-order transition towards synchronization of the phases of the networked units. Our findings constitute the first prove of this kind of synchronization in practice, thus opening the path to its use in real-world applications.