In this paper, various nanostructured poly(aniline) (PANI) particles have been prepared via redox polymerization of aniline in the presence of tri(ethylene glycol) bis(1,5-dihydroxy-naphthalene-2,6- disulfate) ether (TBE). The morphology evolution of the resulting PANI particles was carefully monitored by electron microscopy, clearly underlining the structure-directing role of TBE during the agglomeration of PANI primary nanoparticles (NPs) in the course of polymerization. Various interactions exerted on the PANI primary NPs were assessed based on extended Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, and the thermodynamic balance of these interactions was used to analyze the effect of the TBE concentration on the morphology of the nanostructured PANI particles.