Four types of alkenyl organocopper(I) aggregates linked by 1,3-butadienyl and/or 1,3,5,7-octatetraenyl moieties were selectively realized in good isolated yields. All these organocopper(I) aggregates were structurally characterized by single-crystal X-ray structural analysis. These unprecedented aggregates, stabilized by multiple Cu-Cu interactions and the conjugated 1,3-butadienyl or 1,3,5,7-octatetraenyl bridges, could undergo controlled structural transformations. The 1,4-dicopper 1,3-butadienyl aggregate 3 could be efficiently transformed to aggregate 2, while LiI could disaggregate the 1,3-butadienyl-1,3,5,7-octatetraenyl aggregate 4 to 1,3,5,7-octatetraenyl aggregate 5 and 1,3-butadienyl aggregate 2. Preliminary reaction chemistry and synthetic applications of these organocopper(I) aggregates were also investigated.