A new route to ladder-type pentaphenylenes has been developed in which both good hole-accepting p-type and electron-accepting n-type materials can be prepared from a common intermediate. This key intermediate is a pentaphenylene diester 5 obtained in high yield by Suzuki coupling of 2 equiv of fluorene boronates with 2,5-dibromoterephthalate. Addition of aryllithium followed by ring closure with boron trifluoride produced a blue-emitting ladder-type pentaphenylene. Bromination followed by reductive polymerization with nickel(0) gave new high molecular mass polymers, which show efficient blue emission with a very small Stokes shift. These polymers bridge the gap in emission between polyfluorenes and fully ladder-type polyphenylenes. An alternative ring closure of the dibromopentaphenylene diester 14 with acid made a diketone that is a good electron-accepting material, as it displays a reversible two-electron reduction. The reduction onset potential of -0.875 V against Ag/Ag(+) corresponds to a lowest unoccupied molecular orbital (LUMO) energy level of 3.53 eV, comparable to the work function of magnesium, suggesting that this unit could be used to greatly increase the injection of electrons into polymers containing it in a light-emitting diode (LED) or solar cell. A red-emitting material was prepared by Suzuki coupling of the dibromopentaphenylene 10b with a perylene dye, thus offering the prospect of tuning the emission from pentaphenylene materials over the whole visible range by attachment of suitable dyes. Unoptimized single-layer organic LEDs that used 11b showed stable pure-blue emission with brightnesses of over 200 cd/m(2) at 7 V, with moderate efficiencies.