The combination of pi-stacked with pi-conjugated building blocks offers an essential strategy to construct multifunctional organic semiconductors (MOSS) with the unique optoelectrical properties. Covalent hybrids can efficiently avoid the intrinsic phase-separation defects in corresponding blend system. In this contribution, poly(vinylcarbazole) tethered with terfluorene, PVK-TF, as a double-channeled pi-stacked and pi-conjugated hybrid (SCH), has been constructed via Friedal-Crafts click postmodification (FCCP). The chemical structure and optoelectrical property were determined by GPC, UV-vis, PL, TGA, DSC, and CV Its PL spectra in the annealing thin film at N-2 atmosphere without low-energy emission bands centered at the 530 nm indicates that no pi-stacks between carbazole and TF or among TFs dominate the whole condensed phase, which is in agreement with the intrachain T-shaped pi-pitched motifs in molecular modeling simulation due to steric hindrance effect in complicated diarylfluorenes (CDAFs). A supporting prototype stable deep-blue PLED was successfully obtained with an Internationale de l'Eclairage (CIE) coordinates of (0.20, 0.10) and a width at half maximum (FWHM) of about 60 nm at high current density of 100 mA/cm(2) (35 V). Deep-blue PVK-TF is a promising MOS for hole-transporting and host materials. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47:5221-5229, 2009