A series of silver(I) camphorsulfonato complexes containing various phosphine ligands having the stoichiometry [Ag(camphSO3)(PR3)] [PR3 = PTA (1,3,5-triaza-7-phosphaadamantane), PASO2 (2-thia-1,3,5-triaza-7-phosphaadamantane-2,2-dioxide), PPh3, PCy3, P(CH2CH2CN)3, PPyPh2, or P(o-tol)3] were prepared and fully characterized by NMR spectroscopic methods and X-ray crystallography. Depending on the nature of the phosphine, a variety of different supramolecular structures, including dimers, macrocycles, and coordination polymers, were observed in the solid state. The in vitro antimicrobial activity in seven different pathogens (Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Acinetobacter baumannii, Candida albicans, and Cryptococcus neoformans var. grubii) as well as toxicity in human cells was also examined. While all compounds show some activity against the bacteria, they were especially active against the fungus C. neoformans. The most active and at the same time least toxic compound was found to be the water-soluble complex [Ag(camphSO3)(PTA)2].