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Evidence on the association of 25‐hydroxyvitamin D (25[OH]D) and obesity during the first 5 years of life is limited in China. The objective of this study was to examine the associations between weight, weight for age z score (ZWAZ), weight for length/height z score (ZWHZ), and body mass index for age z score (ZBMI) and 25(OH)D. This was a large population‐based cross‐sectional multicenter study in which the children aged 0–5 years were recruited from 12 children's healthcare centers by a stratified cluster random‐sampling method in 10 cities of the Jiangsu province, China. The 25(OH)D concentration was determined by ELISA. A total of 5289 children were investigated. For 0–71 months children with obesity and nonobesity, the prevalence of vitamin D deficiency was 36.0% and 29.8%, and the 25(OH)D level was 59.8 and 64.0 nmol/L, respectively, and there were all significant difference. Compared with children with nonobesity, children with obesity had higher risk of vitamin D deficiency (OR [95% CI]: 1.33 [1.02, 1.72], p <.05), and had lower 25(OH)D level (β = −3.84, 95% CI = −7.58, −0.09, p <.05). The results for children aged 24–71 months were similar to those for children aged 0–71 months. However, no significant difference was observed in children aged 0–23 months. Vitamin D deficiency was observed in children with greater adiposity during the first 5 years of life. However, the results mainly came from those in the age group of 2 to 5 years instead of the first 2 years in their lives. [ABSTRACT FROM AUTHOR]