Diels-Alder reaction of dienes and in situ generated quinones was accelerated on a PTFE-fiber in an electrolytic lithium perchlorate / nitromethane system. In the presence of PTFE-fiber on a glassy carbon electrode, unstable quinones were efficiently generated by electrooxidation and trapped by dienes maintained on the poly-fluorinated fiber to give the desired cycloadducts stereoselectivity in excellent yields.