ABSTRACT This study aimed to determine the presence of B-complex vitamins and some physicochemical parameters in bee pollen samples from the southern Brazilian states of Paraná, Santa Catarina and Rio Grande do Sul and, then, to identify their correlations with the geographical and botanical origin of the samples using multivariate statistical techniques. B-complex vitamins were determined by HPLC and mean contents were 0.79 mg/100 g (vitamin B1), 0.88 mg/100 g (vitamin B2), 5.31 mg/100 g (sum of vitamin B3 vitamers) and 4.42 mg/100 g (sum of B6 vitamers). The physicochemical parameters of the samples were consistent with those reported in the literature. The results showed that bee pollen is an important source of B-complex vitamins and multivariate statistical exploratory techniques suggested its nutritional content should be evaluated locally.