This report describes the first application of a cyclobutanol ring-opening procedure in the Catellani termination reaction, which includes two β-carbon elimination processes. This tandem reaction features mild conditions, high yields, good functional group tolerance, and a broad substrate scope. Meanwhile, four types of electrophiles (N-benzoyloxyamines, alkyl iodides, aryl bromides, and benzyl chlorides) are quite compatible with this termination reaction for the construction of various types of polysubstituted aromatic hydrocarbons.