Poly(p-phenylene) (PPP) microtubules with diameters of 0.20.8 mm and lengths of ~10 mm have been synthesized by direct oxidation of benzene in the mixed elec-trolyte of boron trifluoride diethyl etherate (BFEE) and trifluoroacetic acid (TFA) (BFEE︰TFA= 2︰1, by volume), containing a certain amount of sodium dodecylbenzene- sul-fonate (SDBS) as surfactant. The microtubules were grown vertically on the working electrode surface. The tubular morphology has been confirmed by scanning and transmis-sion electron microscopies and the chain structure of the skin of the tubules has been characterized by Raman spectros-copy. The electrode property, monomer/surfactant molar ratio and the value of applied potential have strong effects on the morphology of the microtubules. Poly (p-phenylene) (PPP) microtubules with diameters of 0.20.8 mm and lengths of ~ 10 mm have been synthesized by direct oxidation of benzene in the mixed elec-trolyte of boron trifluoride diethyl etherate (BFEE) and trifluoroacetic acid (TFA ) (BFEE: TFA = 2: 1 by volume), containing a certain amount of sodium dodecylbenzene-sul-fonate (SDBS) as surfactant. The microtubules were grown vertically on the working electrode surface. and transmis-sion electron microscopies and the chain structure of the skin of the tubules has been characterized by Raman spectros-copy. The electrode property, monomer / surfactant molar ratio and the value of applied potential have strong effects on the morphology of the microtubules.