This study aimed to assess an eligible cut-off value of anti-Müllerian hormone (AMH) to detect ovarian senescence in a group of premenopausal Greek women to evaluate the possible link between AMH-values and the severity of climacteric symptoms during a follow-up of 24 months. This study included 180 women (group A, 96 women of late reproductive stage/early perimenopause; group B, 84 women in late perimenopause). We measured AMH blood levels and assessed climacteric symptoms using the Greene scale. Log-AMH is inversely associated with postmenopausal status. The AMH cut-off of 0.012 ng/mL predicts the postmenopausal status with a sensitivity of 24.2% and specificity of 30.5%. The postmenopausal stage associated with age (OR = 1.320, 95%CI: 1.084–1.320) and AMH (values ≥ vs. <0.012 ng/mL, OR = 0.225, 95%CI: 0.098–0.529,p-value < 0.001). Moreover, the severity of vasomotor symptoms (VMS) was only associated inversely with AMH (b-coefficient = −0.272,p-value = 0.027). In conclusion, AMH levels measured in the late premenopausal period are inversely associated with the time to ovarian senescence. In contrast, AMH levels measured in the perimenopausal period are inversely associated only with the severity of VMS. Therefore, a cut-off of 0.012 ng/mL predicts menopause with low sensitivity and specificity, making it challenging to use in a clinical setting.