In this work, both generation and reduction processes of the a-radicals of lower fatty alcohols were studied by voltarametry in lower fatty alcohols/peroxydisul-fate/phosphate buffer system. Experimental results showed that such three reactions were successively completed at negative potential on mercury electrode surface: (i) sulfate radical anion SO4- was generated electrochemically from one-electron reduction of peroxydisulfate ion S2O82-,(ii) the SO4- oxidized lower fatty alcohols to the corresponding a-radicals and (iii) the a-radicals were reduced in one-electron and one-proton addition to produce their own reduction waves. The apparent free energy △rGm of the a-radicals of lower straight-chain fatty alcohols such as methanol, ethanol, propanol, butanol and pentanol obtained were 107.09, 116.74, 122.53, 126.39 and 129.28 kJ.mol/L, respectively. The proposed method is more simple and convenient than the current approaches based on the radical-chain reaction for studying alcohol oxidation. In this work, both generation and reduction processes of the a-radicals of lower fatty alcohols were studied by voltarametry in lower fatty alcohols / peroxydisul-fate / phosphate buffer system. Experimental results showed that such three reactions were successively completed at at a negative potential on mercury (ii) the SO4-oxidized lower fatty alcohols to the corresponding a-radicals and (iii) the a-radicals were reduced in one-electron and one-proton addition to produce their own reduction waves. The apparent free energy ΔrGm of the a-radicals of lower straight-chain fatty alcohols such as methanol, ethanol, propanol, butanol and pentanol obtained 107.09, 116.74, 122.53, 126.39 and 129.28 kJ.mol / L, respectively. The proposed method is more simple and convenient than the current approaches based on the radical-chain reaction for studying alcohol oxidation.