Regioregular azobenzene-substituted polythiophenic copolymers were prepared by a regiospecific organometallic polycondensation procedure based on a Grignard metathesis reaction. Copolymers with a high content of chromophoric groups in the side chains and a high degree of configurational order of the backbones were obtained. A sample was also functionalized with hydroxyalkyl chains capable of setting up ordered supramolecular structures through hydrogen bonds. The final materials were fully characterized via NMR, IR, elemental analysis, GPC, DSC and X-ray diffraction. Moreover, measurements of NLO activity on polymer films showed the synthetic strategies adopted and monomers used to be correct. Values obtained by the in situ deprotection of the interacting functional groups after the alignment of the chromophorized side chains were very promising, proving the procedure to be suitable for industrial and commercial applications. (C) 2007 Elsevier Ltd. All rights reserved.