Two pyridoxine compounds were found to be formed in a culture filtrate of Aspergillus niger and A. sydowi, when grown in a medium containing sucrose and pyridoxine. Each of the two compounds I and II was obtained as a white powdered preparation by preparative paper chromatography, gel filtration on Toyopearl HW-40S and Sephadex G-10 columns, DEAE-cellulose column chromatography, and lyophilization. Compounds I and II were identified as 5'-O-(beta-D-fructofuranosyl)-pyridoxine and 5'-O-[beta-D-fructofuranosyl-(2-->1)-beta-D-fructofuranosyl]-pyridoxine, on the basis of the various experimental results, viz., elementary analyses, UV, 1H-, and 13C-NMR spectra, products by hydrolysis with acid and yeast beta-D-fructofuranosidase, migration on paper electrophoresis, and Gibbs reaction in the presence and absence of boric acid. Levansucrase from Microbacterium laevaniformans and yeast beta-D-fructofuranosidase did not catalyze the beta-D-fructofuranosyl transfer from sucrose to pyridoxine to give rise to beta-D-fructofuranosyl-pyridoxine.