This article reports on the comparative study of the hot deformation behaviour of virgin (steel A) and rejuvenated heat treatment creep-exhausted (steel B) P91 steels. Hot uniaxial compression tests were conducted on the two steels at a deformation temperature range of 900–1050 °C and a strain rate range of 0.01–10 s−1 to a total strain of 0.6 using Gleeble® 3500 equipment. The results showed that the flow stress largely depends on the deformation conditions. The flow stress for the two steels increased with an increase in strain rate at a given deformation temperature and vice versa. The flow stress–strain curves exhibited dynamic recovery as the softening mechanism. The material constants determined using Arrhenius constitutive equations were: the stress exponent, which was 5.76 for steel A and 6.67 for steel B; and the apparent activation energy, which was: 473.1 kJ mol−1 for steel A and 564.5 kJmol−1 for steel B. From these results, steel A exhibited better workability than steel B. Statistical parameters analyses showed that the flow stress for the two steels had a good correlation between the experimental and predicted data. Pearson’s correlation coefficient (R) was 0.97 for steel A and 0.98 for steel B. The average absolute relative error (AARE) values were 7.62% for steel A and 6.54% for steel B. This study shows that the Arrhenius equations can effectively describe the flow stress behaviour of P91 steel, and this method is applicable for industrial metalworking process.