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We investigate effects of the local structure on the excitonic transport in C60 thin films by means of temperature-dependent photoluminescence quenching studies in a range of 5 to 300 K. Exciton motion in the X-ray amorphous layers indicates thermally activated transport initiated above 80 K accompanied by a thermalization of excitations into low lying states within the excitonic density of states. Discontinuities in the temperature-dependent photoluminescence behavior can be attributed to a continuous phase transition at 80 K and a first order phase transition at 180 K, thereby revealing structural information on the local film morphology in the C60 films.