A new cationic polythiophene derivative poly[3-(1,1 ′ -dimethyl-4-piperidinemethylene)thiophene-2,5-diyl chloride] (PDPMT-Cl) is synthesized and applied as a colorimetric and fl uorometric probe for the detection of iodide ion and anionic surfactants with high selectivity and sensitivity. Upon adding iodide ion or anionic surfactant into the aqueous solution of PDPMT-Cl, the maximum absorption of the polymer is blue-shifted with a naked-eye color change from red-violet to yellow, signifying that iodide ion or anionic surfactants can cause the dissociation of PDPMT-Cl aggregates. More sensitive results are obtained in the fl uorometric detection to iodide ion or anionic surfactant, thereinto, the detection limit to surfactants can be extended to the order of 10 − 9 M . applied to colorimetric probes for the detection of various bioanalytes. [ 1 − 8 ] However, few of them can be used to detect anionic substrates and the number of colorimetric sensors available at present for anionic substrates remains quite limited. The well-known anionic substrates detection techniques, such as capillary electrophoresis, [ 9 − 15 ] ion chromatography, [ 16 ] normal Raman spectroscopy, [ 17 ] gas chromatography/mass spectrometry (GC-MS), [ 18 ] highperformance liquid chromatography (HPLC), and fl uorescent detection (based on synthetic receptors), [ 19 , 20 ] to some extent, exist some limitations, including time-consuming, requiring expensive equipment, poor selectivity, and sensitivity. Therefore, it is the need of the hour to design new approaches that could improve simplicity, selectivity, and sensitivity.Many systems capable of recognizing, sensing, and transporting negatively charged species are based on supramolecular chemistry. Miyaji et al. [ 21 ] ever reported colorimetric detection of anions by calix[4]pyrrole, but it couldnot monitor the exact concentration, resulting in the limitation of its application. Moreover, though using polymeric membranes doped with various metalloporphyrins or polypyrroles to detect anions were also reported, [ 22 , 23 ] all of them were not still ideal enough to apply. However, E. Li et al.