Two novel alternating copolymers, poly{9,9-dihexylfluorene-2,7-diyl-alt-2,5dioctyl-3,6-bis(4-phenyl)pyrrol ol[3,4-c] pyrrole-1,4-dione} (P1) and poly{9,9-dihexylfluorene-2,7-diyl-alt-2,5-diocty-3,6-bis(3-phenyl)pyrrol o[3,4-c]pyrrole-1,4-dione} (P2), derived from 9,9-dihexylfluorene and diketopyrrolopyrrole (DPP), have been successfully synthesized through palladium-catalyzed Suzuki polycondensation in good yields. P1 and P2 possess moderate molecular weights and polydispersities, well-defined structures, and excellent thermal properties with an onset decomposition temperature around 400 degrees C. Both P1 and P2 in thin films exhibit red photoluminescence from DPP species exclusively, with peaks at 609 and 616 nm, respectively Cyclic voltammetry studies show that P1 and P2 have low-lying lowest unoccupied molecular orbital energy levels at -3.65 eV and reversible reduction processes, so these polymers may constitute another kind of red-emitting polymer with high electron affinity. Preliminary electroluminescent results of devices with an indium tin oxide/poly(3,4-ethylenedioxythiophene)/polymer/Ba/Al configuration reveal that P1 may be a promising candidate for red emitters with a maximum brightness of 153 cd/m(2) and a maximum external quantum efficiency of 0.13%, whereas the performance of P2 is relatively poor. These differences might originate from dffferent conjugation lengths in their main chain. (c) 2006 Wiley Periodicals, Inc.