Organic inherently conductive polymers, such as those based on polyaniline, polypyrrole and polythiophene, are formed in-situ onto polymeric surfaces that are chemically activated to bond ionically the conductive polymers to the substrates. The polymeric substrate is preferably a preshaped or preformed thermoplastic film, fabric, or tube, although other forms of thermoplastic and thermoset polymers can be used as the substrates for pretreatment using, most preferably, phosphonylation-based processes followed by exposure to an oxidatively polymerizable compound capable of forming an electrically conductive polymer. The resultant conductive surface imparts unique properties to the substrates and allows their use in antistatic clothing, surface conducting films for electronic components and the like, and electromagnetic interference shielding.