Macroporous silver films, ordered or fragmented, were fabricated by electrodeposition of silver into the interstitial spaces of templates formed by polystyrene (PS) latex spheres that had been self-assembled onto bare indium tin oxide (ITO) electrodes or onto gold-coated ITO (ITO/Au) electrodes (in which the electrode had been coated by gold sputtering deposition) from two room-temperature ionic liquids (ILs): N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP-TFSI) and N-butyl-N-methylpyrrolidinium dicyanamide (BMP-DCA), respectively, under normal atmospheric conditions. After electrodeposition of silver, the PS spheres were removed by dissolution in tetrahydrofuran (THF) to leave a macroporous silver structure. The higher wettability of ILs onto PS spheres leads to improved penetration of the ILs into the cavities of the PS templates. Electrodeposition is easier if an electrolyte that has a good penetration into the interstitial spaces between the PS spheres. The macroporous silver electrode exhibited much better electrocatalytic performance with respect to nitrate reduction than a regular silver wire electrode. Quantitative determination of nitrate was also examined.