As for the hydrogen production process via electrocatalytic water splitting, the green and sustainable electro-oxidation of organic molecules at the anode is thermodynamically more favourable than the oxygen evolution reaction (OER). Here, we proposed for the first time to replace the OER process by the oxidation of N-Boc-4-piperidine methanol (BPM), via a parallel reaction, which finally leads to the green production of N-Boc-4-piperidine carboxaldehyde (BPC). The amorphous NiFeO(OH) nanospheres with rich valence states were adopted as the anode catalyst, with creation of more active sites. The gas chromatography results showed that nearly all the BPM converted to BPC after 15 h reaction. The electrochemical tests showed that the Faraday efficiency (FE) approaches nearly 100% when the charge transfer is approximately equal to the theoretical charge. This work reports a new process for the alcohol oxidation, providing a valuable green organic synthesis process.