The present invention relates to a production method of a higher alcohol using pyridoxal phosphate (PLP) based in E. Coli, which comprises a step of inoculating a culture medium containing PLP and copper (Cu) ions with a recombinant E. Coli coexpressing ketoisovalerate decarboxylase (KivD) and alcohol dehydrogenase (ADH) prior to culturing. The PLP of the present invention, by forming a complex with Cu, can catalyze oxidative deamination that converts amino acids into 2-keto acid, wherein 2-keto acid can be converted into a higher alcohol by ADH. Accordingly, by converting an amino acid substrate in the culture medium into 2-keto acid by culturing the recombinant E. Coli coexpressing KivD and ADH in the culture medium containing PLP-Cu complex, and through whole-cell bioconversions capable of continuously producing a higher alcohol, effective production of a higher alcohol can be achieved.
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