The transition-metal-free aryne multicomponent coupling (MCC) involving carboxylic acids initiated by aziridines/azetidines has been reported. The use of aziridines as nucleophiles afforded N-aryl β-amino alcohol derivatives and the application of azetidines as nucleophilic triggers furnished N-aryl γ-amino alcohol derivatives in moderate to good yields. These reactions proceed under mild conditions and result in the formation of a new carbon–nitrogen bond and a new carbon–oxygen bond. The utility of carboxylic acids in aryne MCCs has been demonstrated, and the synthetic potential of phenols as acid surrogates in the present aryne MCCs has been realized.