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Accumulating evidence shows that psychosocial work factors of the demand-control and effort-reward imbalance models may contribute to increase blood pressure (BP). Women are more likely to be exposed to these psychosocial factors than men. Moreover, women spend twice as much time per week performing family responsibilities than men. This study aimed to evaluate the longitudinal association of the double exposure to psychosocial work factors and high family responsibilities in women with BP for a 5-year follow-up.At baseline, the study sample was composed of 1215 working women. Psychosocial work factors were measured using validated scales. Family responsibilities were measured using items related to “the number of children and their age” and “housework and children care.” Ambulatory BP measures were taken every 15 minutes during a working day. Associations between psychosocial measures and BP were examined using analyses of covariance.Women with a double exposure to effort-reward imbalance and high family responsibilities had significantly higher BP means than women not exposed to these factors at baseline (diastolic: +2.75 mm Hg), at 3-year follow-up (systolic: +2.22 mm Hg and diastolic: +2.55 mm Hg), and at 5-year follow-up (systolic: +2.94 mm Hg and diastolic: + 3.10 mm Hg). No adverse effect on BP was observed for the double exposure to the psychosocial work factors of the demand-control model and high family responsibilities.A double exposure to effort-reward imbalance at work and high family responsibilities might contribute to elevated ambulatory BP at work among women. BP elevations related to this double exposure may persist for several years.