The syntheses of trineophyl- (1a) and tri-(-)-menthylstannyl phenylacetylene (1b) as well as that of (E)-1-trineophylestannyl-2-phenylethene (2) and (E)-1-trineophylstannyl-1,2-diphenylethene (3) are described. The hydrostannation of 1a with an excess of trimethyltin hydride led to 1,1,1-tris(trimethyltin)-2-phenylethane (4) and/or 1,1-bis(trimethyltin)-2-phenylethene (5) depending on the reaction conditions.