Neonatal bone mass may potentially be influenced by existing maternal vitamin D (25(OH)D) levels. Few studies evaluated maternal vitamin D deficiency (VDD) with neonatal anthropometrics such as weight, height and head circumference (HC), especially in Greece, which is a Mediterranean country with plenty of sunshine and consequently benefits the synthesis of 25(OH)D. We investigated this potential association in Greece, taking into account the administration or not of prenatal vitamin D supplements. The purpose of our study is to ascertain if there is a possible association between maternal VDD and neonatal specific anthropometric characteristics (weight, height and HC) at birth. If this is confirmed by future clinical studies, it would be of interest to develop a prenatal pregnancy selection program that would detect VDD early or during pregnancy in order to improve fetal-neonatal development in a Mediterranean country like ours. We performed a cross-sectional study on 248 early early term infants (after 37 + 0 to 38 + 6 weeks of gestation) but also on full-term infants (after 39 to 40 weeks of gestation) and their Greek mothers from September 2019 to January 2022. Blood samples of 25(OH)D were taken from the mother at the beginning of labor and cord blood was taken from the newborn. Pregnant women were divided into two groups: those who received or did not receive a normal dose of calcium (500 mg/day) and vitamin D supplements (400-800 IU/day) as instructed by their treating physicians. Our findings revealed a positive association between maternal VDD and low neonate birth weight (LBW) in women receiving vitamin D during pregnancy and no association between maternal VDD and neonatal height or head circumference (HC) at birth. Overall, this study highlighted the association between maternal VDD at the end of gestation and LBW neonates born to mothers who received vitamin D supplementation. We did not find any correlation in two of the three somatometric characteristics studied, height and HC. In any case, more clinical studies are needed to further corroborate any potential association of maternal VDD with other neonatal somatometric characteristics.