Naphthenic acid corrosion of steel is studied in crude oil/aqueous phase system at ambient temperature, using a biphasic stagnant liquid without emulsification, by means of electrochemical measurements and surface analysis. The in-situ electrochemical impedance is assigned to the processes occurring at the aqueous phase. Corrosion occurred only in the region of the aqueous phase, as crater-shaped pits that eventually coalesced, generating a nearly uniform attack in the vicinity of the oil phase. The impedance values, normalized to the aqueous region only, reveal corrosion rate increasing with the ratio of crude oil/water. Despite the localized character of the anodic oxidation, the iron naphthenate corrosion products became partitioned between the two phases. Surface-resolved electrochemical techniques in aqueous solution revealed enhanced activity of the regions pre-exposed to oil.Funda????o de Amparo ?? Pesquisa do Estado de S??o Paulo (FAPESP)Conselho Nacional de Desenvolvimento Cient??fico e Tecnol??gico (CNPq)Coordena????o de Aperfei??oamento de Pessoal de N??vel Superior (CAPES)FAPESP: 13/19903-0; 17/10526-0; 14/13601-2CNPq: 305455/2014-1CAPES: 001; 88881-118836/2016-01