Rubber composites with excellent radiation shielding and flexibility are extremely important to personal protective equipments (PPEs) for protecting workers from radiation hazards, especially for mixed radiations. It is, however, challenging to achieve uniform dispersion of fillers and good compatibility of the interfaces in highly‐filled rubber composites that are closely related to their physical properties. In this article, lead borate@polydopamine (PBO@PDA) core–shell particles are chemically bonded with silicone rubber (SR) for co‐shielding of neutron and γ‐rays. Uniform dispersion of the core–shell particles and good compatibility of the interfaces give rise to enhanced flexibility of the rubber composites. Particularly, the SR composite with 40 wt% PBO particles displays increases of 106% in elongation at break and 490% in tensile strength to neat SR. Furthermore, the mass attenuation coefficient of γ‐rays (105 KeV) reaches 2.35 and the thermal neutron absorption rate (0.025 eV) of is 76.9%. This work takes into account the balance between radiation shielding and flexibility of rubber composites, which provides a facile strategy to fabricate excellent integrated properties of flexible materials for shielding mixed neutron and γ‐rays. Lead borate micro–nano particles chemically bonded with silicone rubber are used to coordinately shield thermal neutrons and gamma rays.