The hot deformation behavior of 21-4N heat-resistant steel was studied by hot compression test in a deformation temperature range of 1000–1180 °C, a strain rate range of 0.01–10 s−1 and a deformation degree of 60%, and the stress-strain curves were obtained. The functional relationship between flow stress and process parameters (deformation degree, deformation temperature, strain rate, etc.) of 21-4N heat-resistant steel during hot deformation was explored, the constitutive equation of peak stress was established, and its accuracy was verified. Based on the dynamic material model, the energy dissipation maps and destabilization maps of 21-4N heat-resistant steel were established at strains of 0.2, 0.4 and 0.6, and processing maps were obtained by their superposition. Within the deformation temperature range of 1060~1120°C and a strain rate range of 0.01–0.1 s−1, there is a stable domain with the peak efficiency of about 0.5. The best hot working parameters (strain rate and deformation temperature) of 21-4N heat-resistant steel are determined by the stable and instable domain in the processing maps, which are in the deformation temperature range of 1120–1180 °C and the strain rate range of 0.01–10 s−1.