Polymer-fullerene bilayer heterostructures are suited to study excitonic processes in conjugated polymers. Excitons are efficiently quenched at the polymer-fullerene interface, whereas the polymer-vacuum interface is often considered as all exciton-reflecting interface. Here, we report about efficient exciton quenching close to the polymer-vacuum interface of spin-coated MDMO-PPV (poly[2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylenevinylene]) films. The quenching efficiency is estimated to be as high as that of the polymer-fullerene interface. This efficient quenching is consistent with enhanced intermolecular interactions close to the polymer-vacuum interface due to the formation of a "skin layer" during, the spin-coating procedure. Ill the skin layer, the polymer density is higher; that is, the intermolecular distances are shorter than in the rest of the film. The effect of exciton quenching at the polymer-vacuum interface should be taken into account when the thickness of the polymer film is on the order of the exciton diffusion length; in particular, in the determination of the exciton diffusion length.