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Abstract Introduction Oxidative stress is linked to the development of gestational diabetes mellitus (GDM). Maternal antioxidant vitamins in early pregnancy may play a role in GDM occurrence. We aimed to investigate the associations of vitamins A and E in early pregnancy with the risk of GDM and to explore whether these antioxidant vitamins can be biomarkers for the early prediction of GDM. Methods We carried out a prospective cohort study conducted in Beijing and enrolled pregnant women (n = 667) with vitamins A and E measurements at 9 weeks (IQR 8–10) of gestation and having one-step GDM screened with a 75-g oral glucose tolerance test between 24 and 28 weeks of gestation. Results The vitamin A levels in early pregnancy were significantly higher in women with GDM than in those without GDM (p < 0.0001) and positively correlated with fasting blood glucose. In multivariate models, vitamin A levels were significantly associated with GDM (OR, 1.46; 95% CI: 1.14–1.88; p = 0.0032) per SD. A significant trend of risk effect on GDM risk across quartiles of vitamin A was observed (p trend = 0.016). No significant association of serum vitamin E with GDM was observed overall. However, a noted trend of protective effect on GDM risk across quartiles of vitamin E/cholesterol ratio was observed (p trend = 0.043). In ROC analysis, the multivariate model consisting of vitamin A and other risk factors showed the best predictive performance (AUC: 0.760; 95% CI: 0.705–0.815; p < 0.001). Conclusions Higher levels of vitamin A in early pregnancy were significantly associated with an increased risk of GDM. Vitamin A has the potential to be a biomarker indicating pathogenesis of GDM.