A novel and convenient electrochemical method has been developed for sensitive determination of melamine (MEL) using ascorbic acid (AA) as the recognition element. The working electrode employed in this method was modified with the nanocomposite of hydroxyapatite/carbon nanotubes to enhance the current signal of recognition element. The interaction between MEL and AA was investigated by fourier transform infrared spectroscopy and cyclic voltammetry, and the experimental results indicated that hydrogen bonding was formed between MEL and AA. Because of the existing hydrogen bonding and electrostatic interaction, the anodic peak current of AA was decreased obviously while the non-electroactive MEL added in. It illustrated that the MEL acted as an inhibitor to the oxidation of AA and the decreasing signals can be used to detect MEL. Under the optimal conditions, the decrease in anodic peak current of AA was proportional to the MEL concentrations ranging from 10 to 350 nM, with a detection limit of 1.5 nM. Finally this newly-proposed method was successfully employed to detect MEL in infant formula and milk, and good recovery was achieved.