Applicability of positron annihilation spectroscopy in probing the microstructural changes in ferritic steels has been investigated with thermal treatment studies on modified 9Cr–1Mo steel, during 300–1273K. Positron lifetime results are compared with those of ultrasonic velocity and hardness techniques with two initial microstructural conditions i.e., normalized and tempered condition as well as only normalized condition. In first case, positron lifetime is found to be sensitive to small changes in metal carbide precipitation which could not be probed by other two techniques. In later case, positron lifetime is found to be sensitive to defect annealing until 673K and in distinguishing the growth and coarsening of metal carbide precipitation stages during 773–1073K. The present study suggests that by combining positron lifetime, ultrasonic velocity and hardness measurements, it is possible to distinguish distinct microstructures occurring at different stages.