Grafting of (Me3Si)(2)N-AuPMe3 on SiO2-(700) leads to the formation of [( SiO)Au-PMe3] located in different surface environments due to the presence or absence of adjacent siloxane bridges, as shown both by P-31 solid state NMR and by its conversion into a mixture of [( SiO)Au-PMe3] and [( SiO)Au(PMe3)(2)] upon exposure to PMe3.