Room temperature ionic liquids, such as N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium bis(trifluoromethylsulfonyl)imide, [N1 1 1 2(OH)][NTf2] and 1-ethyl-3-methylimidazolium ethylsulfate, [C2mim][C2SO4], have been used for the electroreductive intramolecular cyclization of unsaturated bromo derivatives 1 in Ni(II)-catalyzed reactions. Controlled-potential electrolyses led to five-membered-ring compounds in moderate to good yields. Cyclic voltammetry in these ionic liquid systems was also investigated.