We have studied the degradation of the photoluminescence (PL) of a phase-separated-film of a polyfluorene blend, F8BT/PFO, on the submicron length scale using near-field scanning optical microscopy, visualizing the PL of blend compositions that do not exist macroscopically in equilibrium. In the initial scans, the topography and the PL were anticorrelated, as the emission was :dominated,by the PFO-rich phase. This behavior changed at longer illumination times, where the emission was dominated by the F8BT-rich phase; i.e., the topography and PL were correlated. Using macroscopic investigation of the mechanisms. that govern the PL, we could explain the time dependence of the PL spatial distribution: while the degradation of F8BT was driven by photobleaching, both faster absorption degradation and photobleaching processes dominate the degradation of PFO. In addition, we found that energy transfer does not protect the PFO from degradation and does not improve its resistance to oxidation.