The variation in apparent and true activation volumes of 304L SS with true plastic strain has been evaluated at three temperatures (973 K, 1073 K and 1123 K) over the strain rates of 3 × 10−3 s−1, 3 × 10−4 s−1 and 3 × 10−5 s−1. The instantaneous strain rate sensitivity parameter was derived from strain-rate jump tests across different strain levels to estimate apparent activation volume. The values of apparent activation volume were higher at 973 K than at other temperatures. In contrast to the apparent activation volume, the estimated values of true activation volume using internal-stress-based kinetic rate law systematically increase with the increasing temperature from 973 K to 1123 K. The higher flow stress with a larger strain hardening rate at 973 K leads to a lower true activation volume in the steel compared to other temperatures. The model outcomes revealed that the instantaneous strain rate jump-up or jump-down leads to the change in the internal and effective stresses. The observed variations in geometrically necessary dislocation density (GND) and intra-grain reference orientation deviation (GROD) in the substructure substantiated the predicted variation in the internal stress level upon strain rate jump up/down. The true activation volume was estimated for a fixed value of mobile dislocation density (ρm = 5 × 1011 m−2) and for varying mobile dislocation density. Irrespective of ρm values, the estimated true activation volume values for 304L SS were in the order of 102 b3 to 103 b3, thereby implying that the intersection of dislocations coupled with the climb of jogged dislocations is the dominant mechanism during tensile deformation at high temperatures. Based on the analysis using the kinetic rate law with a fixed value of mobile dislocation density, it has been realized that the multiplication of effective stress and true activation volume remains constant across the plastic strain levels for the given combination of strain rate and temperature.