We investigated the photoluminescence (PL) characteristics of a highly soluble, fullerene-containing copolymer in both solution and film states. In solution state, the copolymer showed different PL characteristics depending on the aromaticity of the solvent. The PL from polystyrene segments of the copolymer was strongly quenched in an aromatic solvent, while the PL from fullerene remained unchanged. However, the films cast from an aromatic and a nonaromatic solvent demonstrated very similar PL characteristics, implying that the chain alignment or orientation and packing in the films occur in a similar way irrespective of the solvent.