The effect of 2-butyne-1, 4-diol (BD) on the deposition behavior of the Co-Ni alloy was investigated by linear sweep voltammetry. The results showed that BD could prevent the deposition of the Co-Ni alloy. The effect of BD concentration in the sulfate plating bath, on the structure of the Co-Ni deposit was studied by energy dispersive x-ray spectroscopy, scanning electron microscope, and X-ray diffraction, respectively. As a result, BD could smoothen the deposit surface and decrease the diameter of the grain, but too much of BD was not good for the size of the grain. In general, a hexagonal close-packed (hep) phase of the Co-Ni alloy, with a preferentially oriented (110) plane, was prepared by electrodeposition in the presence of BD. The Co-Ni alloy as a catalyst for the electro-oxidation of ethanol in alkaline medium was investigated by cyclic voltammetry. The deposit plated from the bath containing BD possessed better electro-oxidation of ethanol performance compared with that of the deposit plated from only the sulfate plating bath, but too much of BD was not beneficial for catalytic activity. The Co-Ni film was suitable as a magnetic recording material.