Abstract A vitamin B‐12 chemically modified electrode (CME) was constructed by adsorption of vitamin B‐12 onto a glassy carbon surface. The electrode catalyzes the electrooxidation of hydrazine compounds over a wide pH range. The electrocatalytic behavior of hydrazines is elucidated with respect to the CME preparation conditions, solution pH, operating potential, mobile phase flow rate, and other variables. When applied to liquid chromatographic detection of the analytes, the vitamin B‐12 CME yielded a linear response range over 2 orders of magnitude, and detection limits at the picomole level. The vitamin B‐12 CME offers acceptable catalytic stability in both batch and flow systems.