The roadmap for space exploration foresees longer journeys and further excursions outside low-Earth orbit as well as the establishment of permanent outposts on other celestial bodies, such as the Moon or Mars. The design of spacecrafts and habitats depends heavily on the mission scenario and must consider the radiation protection properties of the structural components as well as dedicated shielding. In fact, short- and long-term effects caused by exposure to cosmic radiation are now considered among the main health risks of space travel. One of the current strategies is to find multifunctional materials that combine excellent mechanical properties with a high shielding effectiveness to minimize the overall load. In this work, the shielding effectiveness of a wide variety of single and multilayer materials of interest for different mission scenarios has been characterized. In the experimental campaign, reference and innovative materials, as well as simulants of Moon and Mars in situ resources, were irradiated with 1,000 MeV/u ⁴He, 430 MeV/u ¹²C and 962–972 MeV/u ⁵⁶Fe. The results are presented in terms of Bragg curves and dose reduction per unit area density. To isolate the shielding effectiveness only due to nuclear fragmentation, a correction for the energy loss in the material is also considered. These findings indicate that the best shield is lithium hydride, which performs even better than polyethylene. However, the technical feasibility of shielding needs to be investigated. The classification of all materials in terms of shielding effectiveness is not influenced by the ion species, but the value changes dramatically depending on the beam energy. The output of this investigation represents a useful database for benchmarking Monte Carlo and deterministic transport codes used for space radiation transport calculations. These findings also contribute to recommendations for optimizing the design of space vessels and habitats in different radiation environments.