A novel fluorene-alt-carbazole polymer host Poly(9,9-dioctyl-9H-fluorene-2,7-diyl-alt-N-tetrahydropyran-3,6-carbazole) (PFCz), composed of N-tetrahydropyran-3,6-carbazole and 9,9-dioctyl-2,7-fluorene in the polymer backbone, was synthesized by Suzuki coupling. The PFCz possesses good thermal stability and proper lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) energy levels to facilitate the injection and transport of electrons and holes. Upon doping with blue, green, and red phosphors, red - green - blue (R-G-B) phosphorescent devices hosted by PFCz have been fabricated and investigated. In contrast to those of blue and green devices, the red devices give better performances with a maximum luminous efficiency of 4.88 cd/A and a maximum power efficiency of 1.85% at 149.84 cd/m2, due to favorable triplet energy level (ET) of PFCz for red phosphor, bis(2-methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) [Ir(MDQ)2(acac)]. Additionally, with different doped concentrations of Ir(MDQ)2(acac), the PFCz-related red devices emit nearly pure red light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.57, 0.38), (0.60, 0.38), (0.61, 0.38), and (0.62, 0.38), which were very close to the standard red (0.66, 0.34) by the National Television System Committee. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 43234.