The present paper describes the experimental campaign executed at the ENEA Brasimone Research Centre aiming at supporting the development of a PbLi/water heat exchanger suitable for the lithium–lead loops of the dual coolant lithium lead and the water cooled lithium lead breeding blankets of the EU DEMO fusion reactor. The experiments were performed in a test section named HERO, installed inside the main vessel of the lead–bismuth eutectic-cooled pool-type facility CIRCE. The test section hosts a steam generator bayonet tube mock-up in relevant scale, which was selected as a promising configuration for DEMO purposes. For the thermal-hydraulic characterization of the component, five tests were executed at different water pressures (6, 8, 12 MPa, two tests at 10 MPa), and liquid metal flow rates (40, 33, 27, 20, 10 kg/s). The experimental outcomes proved the technological feasibility of this novel steam generator and its suitability for the DEMO PbLi loops. The activity was completed with a post-test analysis using two versions of the system code RELAP5. Because the experiments were executed with lead–bismuth eutectic, a scaling analysis is proposed to find the equivalence with PbLi. RELAP5 code was applied to recalculate the experimental data using PbLi as working fluid.