Phosphine-stabilized Au clusters have been extensively studied and are used in various applications due to their unique structural, catalytic, and electronic properties. Triphenylphosphine (PPh(3)) is a key stabilizing ligand in the synthesis of Au nanoclusters. Despite its intense use in nanoparticle synthesis protocols, little is known regarding its surface chemistry, monolayer structure, density, and packing arrangement, all of which are important descriptors of functionality. Here, in contrast to sparse earlier investigations, we report that PPh(3) forms very ordered structures on Au(111). Atomic-scale imaging reveals that monolayer formation is accompanied by a partial lifting of the Au(111) surface reconstruction and ejection of extra Au atoms in the surface layer. Interestingly, these atoms are trapped and stabilized as two-dimensional Au nanoislands within the molecular layer. This behavior is in contrast to thiols, also common capping agents, which tend to remove Au atoms beyond those extra atoms present in the native reconstruction and form vacancy islands on the surface. Our data illustrate PPh(3)'s milder reactivity and reveal a new picture of its packing structure. These results shed new light on the surface chemistry of this important ligand for organic, organometallic, and nanoparticle synthesis.