Objectives: To evaluate a wireless smart phone-assisted (SPA) system that assesses ongoing heart rate (HR) and HR-triggered participant reports of momentary stress when HR is elevated during daily life. This SPA system was used to determine the independent and interactive roles of chronic and momentary work stress on HR reactivity among female managers. Methods: A sample of 40 female managers reported their chronic work stress and wore the SPA system during a regular workday. They provided multiple reports of their momentary stress, both when triggered by increased HR and at random times. Relationships among chronic stress, momentary stress, and HR were analyzed with hierarchical linear modeling. Results: Both chronic work stress (b = 0.08, standard error [SE] = 0.03, p = .003) and momentary work stress (b = 1.25, SE = 0.62, p = .052) independently predicted greater HR reactivity, adjusting for baseline HR, age, smoking, caffeine, alcohol use, and momentary physical activity levels. More importantly, chronic and momentary stress significantly interacted (b = 1.00, SE = 0.04, p = .036); high momentary stress predicted elevated HR only in the context of high chronic stress. Conclusions: Female managers who experience chronic work stress displayed elevated cardiac reactivity during momentary stress at work. The joint assessment of chronic stress and momentary stress and their relationship to physiological functioning during work clarifies the potential health risks associated with work stress. Moreover, this wireless SPA system captures the immediate subjective context of individuals when physiological arousal occurs, which may lead to tailored stress management programs in the workplace.