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<b>Background:</b> Postmenopausal women experience rapid progression of coronary artery disease. Vitamin D deficiency appears to be a modifiable risk factor for cardiovascular diseases. This study aimed to analyze the impact of 25-hydroxyvitamin D3 (25(OH)D) level on the severity of coronary atherosclerosis and its potential cardioprotective effect in postmenopausal women. <b>Material and Methods:</b> The study prospectively recruited 351 women in postmenopausal age undergoing coronary angiography. The severity of coronary atherosclerosis was assessed using the Coronary Artery Surgery Study Score (CASSS). A level of 25(OH)D was measured with electrochemiluminescence. <b>Results:</b> Women with more severe coronary atherosclerosis have significantly lower 25(OH)D serum level (<i>p</i> = 0.0001). Vitamin D (β = −0.02; <i>p</i> = 0.016), hypertension (β = 0.44; <i>p</i> = 0.025), age (β = 0.02; <i>p</i> = 0.003), and history of MI (β = 0.63; <i>p</i> < 0.0001), were shown as CASSS determinants. Age, hyperlipidemia, and history of MI were found to determine the level of vitamin D (all <i>p</i> < 0.05). Women with a three-vessel disease hospitalized due to ACS, with a history of MI, hyperlipidemia and hypertension presented the lowest vitamin D level. <b>Conclusions:</b> Our study showed that lower serum 25(OH)D in postmenopausal women is associated with more significant stenosis in the coronary arteries. Therefore, we suggest considering low vitamin D level as a potential risk factor for coronary artery disease.