The study used the data from the National Health and Nutrition Examination Survey (NHANES) 2007–2014 to analyse the relationship of dietary vitamin B1, B2, niacin, B6, B12 and dietary folate equivalent (DEF) intakes with metabolic syndrome. In the multivariate-adjusted model 2, compared with the lowest quartile of dietary intake, the odd ratios (ORs;95% confidence intervals (CIs)) were 0.73 (0.59–0.91), 0.76 (0.61–0.95), 0.76 (0.59–0.98) and 0.77 (0.62–0.96) for the highest quartile of vitamin B1, niacin, B6 and DFE, respectively. The ORs (95%CIs) for the third and the highest quartile of vitamin B2 were 0.78 (0.61–0.99) and 0.62 (0.47–0.83). A linear inverse relationship was found between dietary vitamin B1, niacin, B6, DFE and metabolic syndrome, and a non-linear inverse relationship was found between dietary vitamin B2 and metabolic syndrome. Our results suggested that higher intake of vitamin B1, B2, niacin, B6 and DFE were all associated with reduced risk of metabolic syndrome.