A CuBr-catalyzed cross-coupling reaction of propargyl bromides with terminal alkynes for the synthesis of 1, n-diynes was investigated. In N,N-dimethylacetamide (DMAc), the cross-coupling reactions of 3-bromo-1-arylpropynes, 3-bromo-1-phenyl-butyne/pentyne with aromatic terminal alkynes in the presence of CuBr and K3PO4 under nitrogen at 40 °C occur to give 1, 5-diaryl-1, 4-diynes having 3-CH2/3-CHMe/3-CHEt/3-CHiPr moieties with high chemoselectivity. Under similar reaction conditions, either the reactions of 3-bromo-1-arylpropynes with aliphatic terminal alkynes or the reactions of 3-bromo-1-alkylpropynes with aromatic terminal alkynes afforded the unexpected unsymmetric 1, 4-disubstituted 1, 3-diynes through one of the alkynyl group shifts to the side conjugating with the aryl group; in these cases, 1, 5-disubstituted 1, 4-diynes could not be obtained at all. In addition, when 3-bromo-1-phenyl-butynes react with aliphatic terminal alkynes bearing a distal phenyl group, the formed 1, 4-diynes are expected not to undergo the alkynyl group shift due to the methyl group at 3-position to form 1, 3-diynes; however, 1, 4-diynes could not be obtained either, and the 1, 5-, 1, 6-, and 1, 7-diynes, by an unprecedented remote alkynyl shift to the side conjugating with the aryl group, were isolated from the reaction mixtures in good yields.