A new structural phenanthroindolizidine, 2,3,6,7-tetramethoxyphenanthro[9,10,3('),4(')]indolizidine, has been synthesized efficiently from pyrrole. An important feature of this synthesis is that intramolecular oxidative coupling and rearrangement of 6,7-bis(3,4-dimethoxyphenyl)-8-methoxy-1,2,3-trihydroindolizin-5-one by using VOF3 and TFA have been achieved in one pot.