The introduction of polar groups in poly(3-alkylthiophene) side chains has the advantage of producing polymers giving stable and transferable monolayers on the water surface. Poly [3-(6-tetrahydropyraniloxyhexyl)]-2,5-thienylene can be transferred onto glass slides giving Langmuir-Blodgett structures exhibiting high orientation in the dipping direction. Dichroic ratios up to 5.3 were observed with an order parameter of 0.68.