Functional surfaces were generated by a combination of enzymes with polymer membranes composed of an amphiphilic, asymmetric block copolymer poly(ethyleneglycol)-block-poly(gamma-methyl-epsilon-caprolactone)-block-poly[(2-dimethylamino)ethylmethacrylate]. First, polymer films formed at the air-water interface were transferred in different sequences onto silica solid support using the Langmuir-Blodgett technique, generating homogeneous monolayers and bilayers. A detailed characterization of these films provided insight into their properties (film thickness, wettability, topography, and roughness). On the basis of these findings, the most promising membranes selected for enzyme attachment. Functional surfaces were then generated by the adsorption of two model enzymes that can convert phenol and its derivatives (laccase and tyrosinase), well known as high-risk pollutants of drinking and natural water. Both enzymes preserved their activity upon immobilization with respect to their substrates. Depending on the properties of the polymer films, different degrees of enzymatic activity were observed: bilayers provided the best conditions in terms of both overall stability and enzymatic activity. The interaction between amphiphilic triblock copolymer films and enzymes is exploited to engineer"active surfaces" with specific functionalities and high efficacy resulting from the intrinsic activity of the biomolecules that is preserved by an appropriate synthetic environment.