Porous polymer electrode assemblies are useful for detection or quantification of various analytes. The porous monolith is prepared by depositing a conductive polymer on the monolith, and the preferred conductive due to the presence of the conductive polymer, the porous matrix having both a porous monolith underlying are prepared. The resulting porous electrode can be used for qualitative and quantitative analysis and the capture and / or release of selected charged substances such as nucleic acids. The pores of the electrode matrix may also be filled by a non-conductive material, it produces an electrode having a large number of discrete conductive surfaces.