The new germylene [(PhMe2Si)(2)N](2)Ge has been prepared and fully characterized, and the oxidative addition of [(PhMe2Si)(2)N](2)Ge and [(Me3Si)(2)N](2)Ge with the well-known germylene trapping reagent benzil (1,2-phenylethane-1,2-dione) has been carried out. The crystal structures of the resulting germanium(IV) benzil adducts Ph2C2O2Ge[N(SiMe2Ph)(2)](2) and Ph2C2O2Ge[N(SiMe3)(2)](2) were obtained. The two adducts are essentially isostructural and both exhibit a pseudo-tetrahedral environment at the germanium atom and a nearly planar environment at the nitrogen atoms of the bis(silyl)amido-ligands.