We developed a rapid method to calculate the average electronic structure properties of large ensembles of conjugated polymer chains sampling their conformational space. This is achieved by using the localized molecular orbital (MO) method to rapidly compute the MOs and their energies for isolated polymer chains and through using a calibration scheme to further correct the obtained energies by comparison with a few accurate calculations. The method is applied to the study of the density of states and orbital localization characteristics for five polymers. It is shown that all key properties of the individual chain related to the charge mobility can be rationalized in terms of the properties of the constituent monomers, their interaction, and the conformational flexibility of the chain. More specifically we identify the features that lead to greater charge delocalization. Finally, we discuss the prospect of using this method for a computational high-throughput screening of conjugated polymers.