The luminescence decay kinetics of polyfluorene copolymers containing fluorenone units randomly distributed along the polymer chain have been studied by steady-state and time-resolved fluorescence techniques in toluene solution. The typical green emission from polyfluorenes containing 9-fluorenone moieties is only observed if the 9-fluorenone group is covalently attached to the polymer. Small-angle neutron scattering (SANS) measurements indicate that, independent of the 9-fluorenone fraction, all the studied copolymers adopt an open wormlike conformation. This prevalent 1-dimensional arrangement confirms that the green emission observed with polyfluorenes is not the result of excimer formation in the typical sandwich-like conformation. Analysis of time-resolved fluorescence decays by the maximum entropy method (MEM) collected at the polyfluorene emission (415 nm) and by global analysis of decays collected at 415 and 580 nm (the 9-fluorenone defect emission wavelength) clearly indicates two different time regimes in the population of the fluorenone defect: one occurring in the time interval of 10 to 30 ps and a second one occurring in the time range from 70 to 200 ps. While the slower process shows a linear dependence with the 9-fluorenone fraction, compatible with a hopping migration process along the polymer chain, the faster process does not show such a dependence and instead suggests a short-range Dexter mechanism. These findings are in agreement with our previous work where the presence of a faster component was suggested. ; http://dx.doi.org/10.1021/ma052505l