In this work we present the synthesis, via the Gilch route, of two polymers: poly(9,9-dioctyl-2,7-fluorenylene vinylene) and poly(2-bromo-5-hexyloxy-1,4-phenylene vinylene), which contain fluorene and push-pull (2-bromo-5-hexyloxy-1,4-phenylene) units, respectively. We also present the synthesis of novel copolymers based on the combination of these materials in different proportions. Using the Gilch route, the synthesis yields varied between 42% and 71%, and the average molar masses varied between 4 x 10(3) g mol(-1) and 70 x 10(3) g mol(-1). The thermal, electrochemical and photophysical properties of these polymers were investigated, and their application as hole transporting materials in organic solar cells, in combination with a fullerene derivative (electron transport material), is also presented. (C) 2011 Elsevier B.V. All rights reserved.