The reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 1,3,5-triaza-7-phosphaadamantane (PTA) and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) leads to the formation of [Au(C6F5)(phosph)] (phosph = PTA, 1; phosph = DAPTA, 2). The compounds are slightly soluble in water and aggregate at higher concentrations, giving rise to the formation of needle- and rodlike structures (1) and well-organized spherical aggregates (2). Compounds 1 and 2 were reacted with AgPF6, giving rise to the formation in all cases of luminescent water-soluble 1:1 Au···Ag heterometallic complexes, as evidenced by X-ray crystal structure determination. The use of different silver salts that differ on the counterion induces changes in the resulting luminescence and aggregation morphology.