Abstract This work conducted systematic studies on the effect of B on the hot ductility behavior of Fe-36Ni alloy over the temperature range of 900–1,200 °C by use of Gleeble-3500 thermal simulator, Thermo-Calc software, transmission electron microscopy and secondary ion mass spectroscopy. The influencing factors and mechanisms are also discussed in the present work. Results show that all the values of area reduction of the investigated alloy samples are below 60 % in the temperature range of 900–1,000 °C, indicating the poor hot ductility of the investigated alloys in this temperature range. When the grain boundary sliding occurs during the hot tensile processes, the fine secondary phase particles at grain boundaries prevent the occurrence of dynamic recrystallization and promote the nucleation and propagation of cracking simultaneously, resulting in the poor hot ductility of the investigated alloys in this temperature range. In the B bearing alloy, the segregation of B atoms around austenite grain boundaries promotes the solute dragging effects at grain boundaries and strongly inhibits the occurrence of dynamic recrystallization, which increases the brittle temperature to 1,000 °C. When the temperature exceeds 1,050 °C, the occurrence of dynamic recrystallization improves the hot ductility significantly. However, the coarsening of recrystallized grains and the formation of inter dendritic cracks decrease the hot ductility of the alloy gradually when the temperature increases from 1,100 °C to 1,200 °C.