Two key parameters for the performance of an organic photovoltaic cell are the exciton diffusion length and the charge carrier mobility. Considering these parameters, columnar liquid crystals, with strong pi-orbital overlap between neighbouring cores, are promising materials. We describe our strategy towards the synthesis of both donor- and acceptor-type materials exhibiting a hexagonal columnar mesophase at the operating temperature range of the cell, including room temperature. We present the alignment behaviour of these materials when submitted to a thermal annealing, and, in particular, an approach to obtain thin open films with homeotropic orientation.