We report the efficacy of the pulse electrodeposition technique for the preparation of Ni with two structure directing agents, viz citric acid and tetrabutylammonium bromide. The electrodes were characterized using FESEM, TEM, EDAX, XRD, XPS and AFM for surface morphology, chemical composition, preferred orientation, oxidation states and surface roughness. In the presence of the structure directing agents, the surface morphologies get modified from pine-cone to sponge-like structures and the relative intensities of the (111), (220), (311) and (222) crystal planes get enhanced. The electro-oxidation of glycerol is investigated using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The electrochemical studies indicate that Ni–CA and Ni–TBr exhibit higher catalytic activity with lower onset potentials of 1.32 and 1.33 V vs. RHE and smaller Tafel slopes of 80 and 84 mV dec⁻¹ than bare Ni. An empirical correlation of the experimental peak current density with the work function of the metals has also been deduced.