Electroactive microcapsules with solid oligomeric shell have been successfully prepared during a dialysis process. In this one-pot method, Pickering emulsion template and self-assembly technology are combined. The CV characterization shows the obtained microcapsules exhibit the unique redox electrochemistry for pure tetra(aniline) (TANI). The SEM results reveal that an oil-in-water emulsion stabilized by carboxylic acid doped TANI (HAc-TANI) particles, i.e. Pickering emulsion, forms at the beginning of dialysis. The FT-IR and UV-vis spectra analysis shows that then the assembled particles are locked by the self-assembly of HAc-TANI molecules on Pickering emulsion surfaces via electrostatic interactions and π-π stacking interactions. The obtained air-dried electroactive microcapsules with robust oligomeric shell can retain their integrity. Therefore, they become more suitable for encapsulating hydrophobic functional molecules in industry applications.