Auration of o‐trimethylsilyl arylphosphines leads to the formation of gold and gold‐silver clusters with ortho‐metalated phosphines displaying 3c‐2e Au‐C‐M bonds (M = Au/Ag). Hexagold clusters [Au 6 L 4 ](X) 2 are obtained by reaction of (L‐TMS)AuCl with AgX, whereas reaction with AgX and Ag 2 O leads to gold‐silver clusters [Au 4 Ag 2 L 4 ](X) 2 . Oxo‐trigold(I) species [Au 3 O] + were identified as the intermediates in the formation of the silver‐doped clusters. Other [Au 5 ], [Au 4 Ag], and [Au 12 Ag 4 ] clusters were also obtained. Clusters containing PAu‐Au‐AuP structural motif display good catalytic activity in the activation of alkynes under homogeneous conditions.