We report here our synthetic approach to acetylenic esters of six different steroids. The use of flash vacuum pyrolysis (FVP) is a very appealing tool for the acetylenic moiety to efficiently cyclize and rearrange which allows access to medicinally and pharmaceutically valuable products. Each substrate was subjected to FVP. The products were analyzed, identified and characterized. Acetylenic esters of aromatic steroids resulted in 2 H - cyclohepta[ b ]furan-2-one, and 2 H -chromen-2-one derivatives, while aliphatic esters afforded unsaturated polycyclic hydrocarbons via elimination of propiolic acid.