A highly chemoselective phosphine-catalyzed Rauhut-Currier reaction between maleimides and enones has been realized under very mild conditions, affording the corresponding cross-coupling products in moderate to excellent yields. On the basis of this reaction, an efficient dual phosphine-mediated one-pot synthesis of bicyclic and polycyclic compounds containing a cyclopenta[c]pyrrole skeleton has been accordingly developed, which features a tandem sequence of intermolecular Rauhut-Currier reaction and intramolecular Wittig reaction.