A polyphenol oxidase (PPO) enzyme electrode constructed by the electropolymerization of a pyrrole amphiphilic monomer-PPO mixture, previously adsorbed on a glassy carbon electrode, is applied for the direct amperometric response of phenol, 3-chlorophenol and 4-chlorophenol. Furthermore, the detection of 2-chlorophenol, several polychlorophenols and pentachlorophenol is carried out by an inhibition process of the bioelectrode functioning. The mechanism of the bioelectrode inhibition is investigated in terms of enzymatic inhibition and polymer fouling. The capacities of this system for the resolution of mixtures of phenolic pollutants are also explored on the basis of the kinetic behavior of the bioelectrode response.