This article considers the prospects of using heat-resistant polyimide boron-containing composites to protect astronauts of manned orbital stations from secondary neutron radiation. Variant calculations are performed regarding neutron and gamma-quanta flux distributions in a polyimide composite material with different boron content used to reduce capture radiation. The dependences of spatial distributions of thermal neutron flux density and the gamma-quanta dose rate in a polyimide composite layer with a boron content of 0 to 5% are obtained. An experimental assessment of the energy distribution of neutron and gamma radiation behind the protective polyimide composite is carried out. The introduction of boron atoms in an amount of 3.0 wt.% shows the absence of bursts of secondary gamma radiation energy in the composite, which is due to the high cross-section of thermal neutron absorption by boron atoms. As a result, with a material layer thickness of 3–10 cm, the gamma-quanta dose rate decreases by 2–3 times. The differential thermal analysis method showed that the upper limit of the working temperature of the polyimide composite is 500 °C. The polyimide matrix filled with boron atoms can find effective application in the development of new radiation-protective polymer materials used in manned orbital stations.