Spectra, kinetics, temperature, and excitation-dose dependencies of phosphorescence and delayed fluorescence intensities in thin films of the conjugated polymer poly(9,9-di(ethylhexyl)fluorene) [PF2/6] have been investigated via time-resolved spectroscopy. The results reflect a limited number of available energy sites (traps) for triplet-excited states in the long time region after laser excitation. Triplets captured in these traps decay mono-exponential with a time constant of several 100 ms. In the first few milliseconds after laser excitation, pronounced delayed fluorescence is observed due to triplet–triplet annihilation. The decay kinetics of the delayed fluorescence obeys a power law at all times in accordance with the framework in which triplets find each other after performing a random walk (hopping) in an energetic disordered media, which is represented by variations of the conjugation length in the polymer.