The autonomic nervous system (ANS) is activated by stress and is closely related to the female menstrual cycle. Women with premenstrual syndrome (PMS) have an imbalanced ANS response in their premenstrual period. However, no studies have explored the reasons for the differences in ANS response among women. In this study, we investigated how the female menstrual attitude and acute social stress influence the ANS response in women with PMS. First, 277 women [24.35 ± 2.1] were selected to measure the mediating role of women’s menstrual attitude between PMS severity and perceived ANS response. Second, participants’ (50 women [23.23 ± 1.25] with and 46 women [22.92 ± 2.00] without PMS) heart rate (HR) and HR variability (HRV; reflecting the functioning of ANS) under social stress were measured during various menstrual cycle phases. The results indicated that menstrual attitude (bothersome and predictable) had mediating effects between the degree of PMS and perceived ANS response; when undergoing a high cognitive load (e.g. mental-arithmetic) task, the ANS of the PMS group demonstrated hypo-arousal and delayed recovery in the late luteal phase; Therefore, menstrual attitude could influence female perceived ANS response, which may be a risk factor for PMS. When women with PMS experience high-strength cognitive pressure in the premenstrual period, their ANS showed hypo-arousal and delayed recovery, which may be another risk factor for PMS.