Polypyrrole (PPy) nanotubes were suggested as functional adsorbents for the electrochemically controlled solid-phase extraction (EC-SPE) of both anions and cations. The preparation of the PPy nanotubes on ITO glass was achieved by using a constant potential method. In situ anion (chloride, nitrate, and sulfate) and cation (dopamine) uptake and release were examined under controlled potential conditions for demonstrating the prospective applications of the PPy nanotube based EC-SPE. It was found that the PPy electrodes cycling between oxidation and reduction potentials could facilitate the extraction and desorption of the anions and cations, respectively. The method was validated with a standard reference material and used for the determination of the ions in real water samples.