Background: Menopause is associated with negative cardiovascular adaptations related to estrogen depletion, which could be counteracted by physical exercise (PhE). However, the impact of total adherence-rate (TA) to PhE and sedentary time (SedT) on cardiometabolic profile in this population has not been elucidated. Methods: For 13-weeks, 43 women (57.1 ± 4.7 years) participated in a 4-days-a-week moderate-intensity walking training. They underwent laboratory, anthropometric and echocardiographic assessment, before and after training (T0–T1). Spontaneous physical activity (PhA) was assessed with a portable multisensory device. The sample was divided according to TA to PhE program: <70% (n = 17) and ≥70% (n = 26). Results: TA ≥ 70% group experienced a significant T1 improvement of relative wall thickness (RWT), diastolic function, VO2max, cortisol, cortisol/dehydroandrostenedione-sulphate ratio and serum glucose. After adjusting for SedT and 10-min bouts of spontaneous moderate-to-vigorous PhA, TA ≥ 70% showed the most significant absolute change of RWT and diastolic function, body mass index, weight and cortisol. TA ≥ 70% was major predictor of RWT and cortisol improvement. Conclusions: In a group of untrained, postmenopausal women, a high TA to a 13-weeks aerobic PhE program confers a better improvement in cardiometabolic profile, regardless of SedT and PhA levels.