(1) Background: This study utilized a 24-week intervention incorporating heart rate sensors for real-time monitoring of intervention training, aiming to comprehensively assess the effects of Tai Chi on vascular endothelial function, atherosclerosis progression, and lipid metabolism. The insights gained may inform personalized non-pharmacological interventions to enhance the management of cardiovascular health in this population to provide sustainable benefits and improve quality of life. (2) Methods: Forty postmenopausal middle-aged and elderly women were randomly assigned to an exercise or control group. The exercise group underwent a 24-week Tai Chi (BaFa WuBu) training intervention with real-time heart rate monitoring using Polar sensors. Pre- and post-intervention assessments included body composition, blood pressure, vascularity, and blood parameters measured with the Inbody 720, Vascular Endothelial Function Detector, and Arteriosclerosis. Data were analyzed using SPSS 26.0 and mixed-design ANOVA to assess the effects of time, group, and their interactions on study outcomes. (3) Results: After training through 24 weeks of Tai Chi (BaFa WuBu) intervention, compared with the control group, systolic blood pressure in the exercise group was significantly lower (p < 0.05), and the difference between left and right arm pulse pressure, left and right ankle mean arterial pressure, left and right side baPWV, left and right side ABI, TC, TG, LDL, and blood pressure viscosity were all very significantly lower (p < 0.01), and the diastolic blood pressure was significantly higher (p < 0.05). Compared with baseline values in the exercise group, systolic blood pressure, right and left arm pulse pressure difference, right and left ankle mean arterial pressure, right and left side baPWV, right and left side ABI, TC, TG, LDL, and blood pressure viscosity decreased very significantly (p < 0.01) and diastolic blood pressure and FMD increased very significantly (p < 0.01) in the exercise group after the intervention. (4) Conclusions: In our study, a 24-week Tai Chi (BaFa WuBu) program significantly improved vascular health in middle-aged and older postmenopausal women. This simplified Tai Chi form is gentle and effective, ideal for older adults. Regular practice led to reduced vascular obstruction, improved lipid metabolism, and enhanced vascular endothelial function, crucial for preventing vascular diseases. The real-time heart rate sensors used were pivotal, enabling precise monitoring and adjustment of exercise intensity, thereby enhancing the study's scientific rigor and supporting Tai Chi (BaFa WuBu) as a beneficial therapeutic exercise.