Grain boundary (GB) engineering is crucial in the austenitic stainless steel (ASS) design for nuclear energy applications. In this work, the influence of different GB structures on radiation defect recombination and radiation-induced segregation (RIS) at different temperatures were investigated using molecular dynamics simulation. Four typical GBs in ASSs were selected as model structures. Results showed that GBs remained stable at various temperatures and they all exhibited better self-healing performance than single crystals in terms of radiation defects. However, except Σ3(112) GB, other three GBs cannot inhibit the radiation induced segregation, while promoting the radiation defect recombination. Calculation results showed that the higher Σ value of GBs can lead to a greater lattice mismatch near GBs, which not only results in stronger sink strength for radiation induced defects, but also provides more sites for solute atoms and causes greater segregations eventually. Owing to the intrinsic low Σ and large inclination angle characteristic, Σ3(112) GB achieves an excellent balance between the defect-absorption and RIS. This phenomenon provides a feasible route for the future GB design in ultra-high radiation tolerant materials.