The structure of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (C4mpyrNTf2) room-temperature ionic liquid at an electrified gold interface was studied using neutron reflectometry, cyclic voltammetry, and differential capacitance measurements. Subtle differences were observed between the reflectivity data collected on a gold electrode at three different applied potentials. Detailed analysis of the fitted reflectivity data reveals an excess of C4mpyr+ at the interface, with the amount decreasing at increasingly positive potentials. A cation rich interface was found even at a positively charged electrode, which indicates a nonelectrostatic (specific) adsorption of C4mpyr+ onto the gold electrode.