Polypyrrole (PPy) microstructures with diverse shapes were synthesized in an aqueous inorganic salt medium including organic crystals and pyrrole (Py). A series of sulfobenzoic acid salt forms with various cations (K+, Na+, Li+, NH4+) in different positions (para, meta, ortho) of the sulfonate group on the benzene ring were used to form organic crystals as sacrificial templates. Using these crystals, we produced five different shapes of PPy microstructures (hexagonal microplates, curled nanofibers, lozenge-shaped microplates, rigid rods, parallelogram microplates), which replicated the shapes of the organic crystal templates through electrostatic interaction between the anionic crystal surfaces and the cationic PPy chains. In contrast, PPy that was polymerized without crystals showed bulky agglomerates of 200 -500 nm size. The electrical properties were dictated by the molecular structures of the organic salt molecules used. While the highest conductivity (200.3 Scrn(-1)) was observed in PPy using crystals of para-linked 4-sulfobenzoic acid monopotassium salt, the lowest conductivity (0.8 Scm(-1)) was observed in PPy prepared in the presence of crystals of ortho-linked 2-sulfobenzoic acid monoammonium salt. (C) 2010 Elsevier Ltd. All rights reserved.