A series of in-situ thermally polymerizable hole-transporting materials based on the triarylamine-containing perfluorocyclobutanes (PFCBs) have been developed and characterized. Electrochemical studies reveal that the energy level of the highest occupied molecular orbital (HOMO) for these materials is between -5.1 and -5.3 eV, which is a good match for the work function of indium tin oxide (ITO), a commonly used anode for organic and polymeric light-emitting diodes. UV-vis absorption, photo-and electro-luminescence spectral studies indicate that aggregates are formed during the thermal polymerization. The PFCB-based materials are very robust after polymerization, which enables the fabrication of multilayer polymer light-emitting diodes. Highly efficient organic and polymer LEDs are demonstrated using these materials as the hole-transporting layer, illustrating the superb performance of the PFCB-based polymers.