Abstract: β-cyclodextrin (β-CD) with a special cavity structure was firstly grafted on the surface of multi-walled carbon nanotubes (MWCNTs), which were then immobilized on Ti plates to obtain the β-CD/MWCNT/Ti substrate. Binary Pd-Ni nanoparticles were electrodeposited on the surface of β-CD/MWCNT/Ti substrate to prepare the PdNi-β-CD/MWCN/Ti electrode; its activity in electrocatalytic oxidation of propanol and butanol isomers in alkaline media was then investigated by voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results indicated that the binary PdNi nanoparticles are highly dispersed with the size of 90~130 nm on the β-CD/MWCNT/Ti substrate. The configuration of alcohols plays a significant role in their electrochemical oxidation activity in alkaline media on the PdNi-β-CD/MWCNT/Ti electrode. For the two propanol isomers, the PdNi-β-CD/MWCNT/Ti electrode exhibits much higher electroactivity for 1-propanol oxidation than that for 2-propanol oxidation. For the four butanol isomers, the electrocatalytic activity of the PdNi-β-CD/MWCNT/Ti electrode towards their oxidation follows the order of 1-butanol > 2-methyl-propanol > 2-butanol >> 2-methyl-2-propanol; the electrode shows almost no electrocatalytic activity in the oxidation of tertiary butanol. The mechanism for the electrocatalytic oxidation of various propanol and butanol isomers was also analyzed by considering the Muliken net charge on the different carbon atoms bonded with hydroxyl –OH, which indicates that the alcohol molecule with lower Muliken net charge value will be more easily oxidized over the PdNi-β-CD/MWCNT/Ti electrode.