Electrooxidation has been used to deposit thin film polyaniline as well as its derivative - thin film poly (ortho-phenylenediamine) (POPD) and poly (meta-phenylenediamine) (PMPD) on carbon electrodes, which are subsequently used to monitor the environmental heavy metal ions (Hg2+, Pb2+ ,Cd2+) through a rather unusual "blocking" of anodic stripping for these metals. Using Hg2+ as a model, its cyclic voltammogram for a modified glassy carbon electrode with the resultant polymer shows an enhanced cathodic peak that increases linearly with the analyte ion concentration. POPD also exhibits unique selective detection for organic species. Acetaminophen and uric acid can be preferentially detected over ascorbic acid from a mixture of these three compounds. In addition, the effect of carbon nanotubes incorporated in polyaniline (PAN) film is observed to have enhanced electrochemical catalytic activities on the remedy of environmental dichromate.