structureless emissions attributed to exciplexes are observed from the N-methylpyrrole systems. Substituted pyrroles (1:1 and 2:1 adducts) are formed from irradiation of the phenylethenes with pyrrole, and 2-styrylpyrroles result from the phenylethynes. Styrene, but none of the other arenes, undergoes photoaddition to N-methylpyrrole in the presence of 10% acetic acid.