Density functional theory calculations were performed to study the competing pathways of rhodacycle intermediates generated in Rh(III)-catalyzed annulations of 2-alkenyl phenols and 2-alkenyl anilides with alkynes. The results show that the multiple pathways of eight-membered rhodacycles can be subtly tuned to give specific cyclic products. The seven-membered oxacyclic and spirocyclic products from 2-alkenyl phenols are formed by favoring the pathway of dissociating the Rh-O bond of O-contained rhodacycles, which are followed by antarafacial nucleophilic attack. The indoline product from 2-alkenyl anilides is generated through the pathway of intramolecular olefin migratory insertion of the N-contained rhodacycle.