A synthetic method to prepare bicyclo[6.3.0]undeca‐2,4,9,trienyl esters efficiently from gold(I)‐catalyzed Rautenstrauch rearrangement/1,5‐hydride shift/8‐endo‐dig cyclization of 1‐ene‐4,10‐diynyl esters is described. The suggested double cycloisomerization mechanism delineates the first example of an unactivated all‐carbon tethered 1,7‐enyne, either preformed or formed in situ, which undergoes an 8‐endo‐dig cyclization pathway to give a cyclooctane motif. It also offers an extremely rare synthetic method in organic chemistry that can sequentially assemble both ring components of the bicyclic motif from an acyclic precursor in one step. [ABSTRACT FROM AUTHOR]