The copper silanechalcogenolates (Bu3PCuESiPh3)-Bu-t ( 1, E = O; 2, E = S; 3, E = Se) were prepared from the reaction of [ (Bu3PCu)-Bu-t( CH3CN)(3)] BF4 with [ Ph3SiELi( THF)(2)](2) in acetonitrile. The compounds were obtained as colorless, crystalline, but thermally labile solids. X-ray crystallography shows that complexes 1 - 3 are monomeric in the solid state with no (CuCu)-Cu-... interactions. The Cu atoms have either a linear or a near-linear coordination geometry in all three complexes. Interestingly, the O atom in complex 1 is also linear, which is in contrast to the highly bent S ( 2) and Se analogues ( 3). Density functional theory calculations suggest that both the linear geometry of 1 and an associated extremely short Cu - O distance [ 1.769( 4) angstrom] are not the result of pi delocalization but are the result of a fine balance of electrostatic interaction and Pauli repulsion.