Sunlight exposure is an essential source of vitamin D for many humans. However, hypovitaminosis D is a global public health problem. This study aimed to develop and validate a sun exposure score (SES) and correlate it with serum 25-hydroxyvitamin D levels in women of childbearing age. One hundred and sixty women aged 18 to 45 years residing in Meknes, Morocco, were included. A questionnaire estimating the sun exposure score and blood analysis of serum 25-OHD concentration were performed. The questionnaire’s reliability and construct validity were evaluated using Cronbach’s alpha and factor analysis. Spearman’s test was used to assess the correlation between SES and 25-OHD levels. The score’s reliability and construct validity were good, with Cronbach’s alpha values >0.70 and factorial saturation ranging from 0.696 to 0.948. Serum 25-OHD levels were significantly associated with the total sun exposure score, and all SES domains (Rho was 0.615 (p < 0.0001), 0.307 (p < 0.0001), 0.605 (p < 0.0001), and 0.424 (p < 0.0001) for total SES, indoor exposure domain, outdoor exposure domain, and sun protection practice domain, respectively). In addition, median 25-OHD levels increased significantly when sun exposure was changed from insufficient to sufficient (p < 0.0001). The results suggest that the sun exposure score could be used as a clinical tool to assess vitamin D levels in women of childbearing age.