Time-resolved photoluminescence studies reveal distinct differences between the recombination processes in a chalcogenide glass and in its crystalline counterpart. Here the three luminescence bands of a-As2S3 are interpreted in terms of the recombination of an excition, a self-trapped exciton and a pair of electron- and hole-like small polarons. The two luminescence bands observed in the crystal are attributed to the recombination of two types of excitons composed respectively of a hole bound to a self-trapped electron, and a hole which is induced to self-trap in the presence of a self-trapped electron.