Degradation-induced changes in the structural and optical properties of the polyfluorene-based blue emitting films and LEDs are examined using spectroscopic (FTIR, UV-vis, photo- and electroluminescence), analytical (FTIR and ESCA), and scanning probe microscopy techniques. The materials studied are oligomers (DP similar to 10) of 9,9-di-n-hexylfluorene and its random copolymer with anthracene. In situ FTIR monitoring is used to characterize chemical changes in the active layer of operating LED devices. Two primary mechanisms of degradation are identified. In the first, photooxidation of the polymer matrix leads to the formation of an aromatic ketone, most likely fluorenone at the chain terminating monomer units, which quenches the fluorescence. The second process promotes aggregate formation, which then leads to loss of luminous intensity by exciton transfer and relaxation through excimers.