With aldehydes as a CO source under solvent-free conditions, rhodium complex efficiently catalyzedan intramolecular carbonylative alkene−alkyne coupling (Pauson−Khand-type reaction) and variousbicyclic enones were obtained in high yield. Experiments under argon flow and a 13C-labelingexperiment suggested that almost no free carbon monoxide was generated in this reaction. Whennoncationic rhodium complex with chiral phosphine was used as a chiral catalyst, the reactionproceeded enantioselectively to give various chiral cyclopentenones in up to 90% ee under solvent-free conditions.