This paper reports the microwave mediated direct synthesis of N-phenylmaleimide (3) from maleic anhydride (1) and aniline (2) by using microwave irradiation. Good yields and very short reaction times were the main aspects of the method. The reaction conditions and kinetics of this process were investigated. Microwave irradiation in a boiling solvent showed the existence of a significant specific microwave effect. The microwave homopolymerization of 3 in bulk using 2,2'-azoisobutyronitrile (AIBN) as a free radical initiator was also carried out.