The photoreaction of maleimide, one of the best model compounds of DNA molecules for psoralen-DNA photoreactions, is studied in order to investigate the photoreactivity and the mechanism of the maleimide-psoralen photoreaction. The (2+2) photocyclodimer of maleimide was obtained in solution state by direct or sensitized irradiation. The rate constant of dimerization is determined by quenching studies and found to be of the order of $10^9 M^{-1}sec^{-1}$. The direct dimerization of maleimide is found to undergo through the triplet excited state. The quantum yields of dimerization are dependent on the maleimide concentration.