Placental calcification is an aging process that is increasingly linked to adverse pregnancy outcomes when it occurs prematurely. Vitamin D has immunomodulatory properties and may play a role in placental calcification. This study explored the association between maternal vitamin D, inflammatory cytokines, and placental calcification. A total of 46 pregnant women aged 16–40 years were included in this study. They were divided into four groups: Group 1 (control group; n = 10, without placental calcification), Group 2 (n = 12, Grade 1 placental calcification), Group 3 (n = 12, Grade 2 placental calcification), and Group 4 (n = 12, Grade 3 placental calcification). Serum vitamin D (25(OH)D) and cytokine (TNF-α, IL-2, IL-4, IL-10) levels were measured by ELISA, while serum calcium levels were measured by colorimetric analysis. Vitamin D levels declined gradually with increasing placental calcification ( p = 0.0146 for G3 vs. control). Calcium levels did not differ significantly across groups ( p > 0.05). The pro-inflammatory marker TNF-α was significantly increased in G3 compared to the control group ( p = 0.016). Similarly, IL-2 levels increased, but the difference was not statistically significant. In contrast, anti-inflammatory cytokines IL-4 and IL-10 decreased, with IL-10 showing a significant positive correlation with vitamin D levels ( r = 0.8403, p = 0.0006). These findings suggest that vitamin D deficiency may play a significant role in placental calcification, mediated by elevated pro-inflammatory cytokine TNF-α and reduced anti-inflammatory cytokine IL-10.