Shape-controllable polyaniline (PANI) microstructures with a unique tetragonal star-like morphology were synthesized by a rapid initiated strategy with glycine (Gly) as dopant. The results demonstrate that the morphology of PANI microstructures is significantly influenced by the molar ratio of aniline to glycine. The PANI prepared in this study exhibits nanofiber-like morphology with exceptionally high crystallinity. These nanofibers can self-assemble into tetragonal star-like microstructures with a unique alignment. The chemistry, morphology, and crystal structure of glycine doped star-like microstructures were studied using SEM, UV–vis, FT-IR, XRD and cyclic voltammetry (CV).