N-oxide forms of three vitamin B_6,pyridoxine, pyridoxamine and pyridoxal, were prepared in crystalline forms as follows : Pyridoxine N-oxide was obtained by oxidation of pyridoxine base with hydroperoxide in glacial acetic acid. Pyridoxal N-oxide was prepared by oxidizing pyridoxine N-oxide with colloidal manganese dioxide and sulfuric acid. Oxidation of triacetyl derivative of pyridoxamine with hydroperoxide, followed by hydrolysis, yielded pyridoxamine N-oxide. These N-oxides easily returned to the natural forms of the vitamin with catalytic reduction.