Polycondensation of 1-(2-pyrimidinyl)pyrrole with 2,7-dibromo-9,9-dioctylfluorene via Ru-catalyzed direct arylation gives the corresponding conjugated polymer with a molecular weight of 19 800 in 86% yield. The introduction of directing group, 2-pyrimidinyl substituent, into the pyrrole monomer induces ortho-metalation and provides the site-selective direct arylation polycondensation at the alpha-position of pyrrole unit without the protection of beta-position. The removal of 2-pyrimidinyl substituent on the pyrrole unit proceeds efficiently and results in the enhancement of coplanarity along the main chain of the polymer.