Polyaniline (PANI) microtubes with a hexagonal cross-section are successfully synthesized by a self-assembly process in the presence of 8-hydroxyquinoline-5-sulfonic acid (HQS) as a dopant and FeCl3 as an oxidant. The wall thickness of the PANI/HQS microtubes can be adjusted by the content of the oxidant. It is proposed that the aniline/HQS salts serve as a hard template for the formation of the hexagonal-cross-section microtubes. Moreover, PANI/HQS microtubes combined with ZnSO4 show pH-dependent fluorescence. PANI hexagonal-cross-section microtubes combined with a pH-sensitive fluorescence may promise potential applications in fields such as chemical sensors and confined reaction vessels.