The application of nuclear technologies simulates the development of radiation shielding materials. Traditional heavy-weight concrete used for radiation shielding is limited in practical construction due to the poor mechanical properties and durability. This study developed a PVA fiber-reinforced ultra-high performance concrete (UHPFRC) with magnetite as heavy aggregates used for radiation shielding. Due to the scientific skeleton design, UHPFRC exhibits superior mechanical properties, with compressive strength and flexural strength reaching up to 121.9 MPa and 23.2 MPa, respectively. The microstructure of UHPFRC was investigated in detail and the results revealed that the incorporation of PVA fibers refined the pore structure of UHPFRC. The interfacial transition zone between magnetite aggregates and cementitious matrix in UHPFRC was much denser than that in traditional concrete due to the low water to binder ratio. The gamma and neutron radiations shielding capacity of UHPFRC were evaluated by the combination of actual measurement and simulation. By introducing light nuclei and refining the pore structure, the incorporation of PVA fibers improved the neutron radiation shielding capabilities of UHPFRC by 5.1%.