We report on first ab initio results concerning the photodesorption of CO from a single C-60 fullerene. The weak interaction makes the use of computationally demanding electron correlation methods mandatory and we present various approaches for reducing the computational effort. The calculated adsorption energy amounts to -8.5 kJ mol(-1) for the electronic ground state. The photodesorption is assumed to result from a 5 sigma -> 2 pi(star) excitation in the adsorbate. The interaction in the excited state is stronger and leads to an Antoniewicz-like desorption mechanism. We treated the desorption process quantum dynamically and calculated desorption probabilities and velocity distributions of the desorbing molecules. (C) 2011 Elsevier B.V. All rights reserved.