Pain catastrophizing is a prominent psychological factor that exhibits a robust correlation with pain. Although the complex property of pain catastrophizing was reported to vary across different pain phases, the contribution of chronic pain in its progression from general trait to a higher state remains unclear. The objective of this study is to examine the neural mechanism and degree to which pain catastrophizing is reinforced in the context of primary dysmenorrhea (PDM), which is one of the most prevalent gynecological complaints experienced by reproductive women. 29 women with moderate to severe PDM were included in this study. Arterial spin labeling was utilized to quantify the cerebral blood flow (CBF) for each subject in both pain-free and painful phases. The pain catastrophizing scale (PCS) was completed in two phases and the Short-Formed McGill Pain Questionnaire was completed in the painful phase. Compared to the pain catastrophizing in pain-free phase (PCS_pf), the pain catastrophizing in the painful phase (PCS_p) is higher and positively correlated with the compositive factor of menstrual pain. CBF analysis indicates the PCS_p is positively associated with the CBF of frontal cortex, hippocampus and amygdala. The reinforcement of pain catastrophizing is correlated with the CBF of prefrontal cortex. Specifically, the medial prefrontal cortex, which correlates with pain state as well, plays a crucial role in mediating the reinforcing effect of pain on PCS_p. These results promote both the phenomenological and mechanical comprehension regarding pain catastrophizing management in individuals with chronic pain.