This work establishes a new method to measure the electrochemically active surface area (AECSA) of nickel electrodes, in situ. The addition of 0.08 mol L−1 of an oxalate salt to an alkaline electrolyte solution shifts the half-wave potential of the Ni(II)/Ni(III) redox pair by about −80 mV. Further, these peaks are very narrow. The sharpest peak in this work has a full width at half maximum (FWHM) of just 11 mV. This unusual sharpness is attributed to the layered structure of nickel hydroxides and the adsorption of oxalate from the solution on the (001) surface. This is supported by attenuated total reflectance infrared (ATR-IR) peaks measured at 1265 cm−1, 1655 cm−1, and 1713 cm−1, which correspond to mononuclear bidentate oxalate bonded to nickel. At sufficiently fast potential scan rates (≥150 mV s−1), the adsorbed oxalate limits growth of the surface hydroxide to a single layer. During the reverse scan, the surface NiOOH/Ni(OH)2 reduction peak is well-separated from other electrochemical processes and may be used to accurately and precisely measure the AECSA. The error of this method is estimated at < 10%.