A new rigid rod-like phenolic pi-conjugated polymer containing pillar[5] arene units in its main chain was prepared. First, a pillar[5] arene-containing pi-conjugated polymer was prepared by Pd-catalyzed copolymerization of 4,4 '-diphenyldiboronic acid with a pillar[5] arene bearing two triflate moieties in one hydroquinone unit and eight ethoxy groups in the other units. Then, deprotection of the ethyl moieties using BBr3 gave a rigid rod-like phenolic pi-conjugated polymer. The phenolic polymer showed high thermal stability, with a 10 wt% loss temperature (T-10) of 300 degrees C in a nitrogen atmosphere, which is higher than that of a pillar[5] arene containing 10 phenolic moieties (T-10 = 164 degrees C). Moreover, the phenolic pi-conjugated polymer showed selective gas adsorption properties: it was highly selective for the adsorption of CO2, but did not take up N-2 or methane. (C) 2017 Elsevier Ltd. All rights reserved.