Objective: The present study aims to measure docosahexaenoic acid (DHA) in both the plasma and erythrocyte of a child population and compares them with respect to their associations with dietary and metabolic risk patterns. Methods: A cross-sectional study was conducted, and a total of 435 children ages 5–7 years old were recruited. Diet information was collected using a food frequency questionnaire (FFQ). The physical indicators, blood pressure, and glycolipid metabolic indicators were determined. The plasma and erythrocyte DHA were analyzed using a gas chromatography mass spectrometer. Principal component analysis was used to identify dietary and metabolic risk patterns. Multivariate regression analyses were used to investigate the associations of DHA status with dietary and metabolic risk patterns. Results: A significant correlation between plasma and the erythrocyte DHA concentration was found (r = 0.232, p < 0.001). A diversified dietary pattern characterized that a high intake of diversified foods had a positive association with the plasma DHA level (β = 0.145, 95% CI: 0.045~0.244, p = 0.004). Children of obesity risk patterns with a high weight, pelvis breadth, BMI, upper arm circumference, and chest circumference had lower plasma DHA concentrations (OR = 0.873, 95% CI: 0.786~0.969, p = 0.011). Children with higher plasma and erythrocyte DHA concentrations were adhered to blood lipid risk patterns with high CHOL and LDL-C levels. The plasma DHA (OR = 1.271, 95% CI: 1.142~1.415, p < 0.001) had a stronger association with a blood lipid risk pattern than erythrocyte (OR = 1.043, 95% CI: 1.002~1.086, p = 0.040). Conclusions: The diversified dietary pattern had a higher plasma DHA concentration. Lower levels of plasma DHA were positively associated with obesity in children. DHA in plasma appears to be more strongly associated with blood lipid metabolism than erythrocyte. Plasma DHA may be a more sensitive bidirectional biomarker to evaluate the recently comprehensive diet intake and metabolic risk of children.