A novel solid-phase microextraction coating based on the electropolymerization of a molecular receptor properly functionalized with 2,2'-bithiophene was developed for the determination of environmental pollutants in air and water samples. The 2,2'-bithiophene-based film was electrochemically deposed on the surface of a gold wire using cyclic voltammetry. The fibres showed a porous structure with an average thickness of 12+/-3 microm (n=5): a good intra-batch and inter-batch repeatability with RSD lower than 14% was also observed. The selective interactions via hydrogen bonding with organic molecules containing electronegative atoms was proved: LOD values in the low ng/l range allowed the determination of vinyl chloride and chlorobenzenes at trace levels in environmental matrices.