Four Cu^I and three Ag^I mixed–ligand complexes containing a heterocyclic pyrimidine-type thione (pymtH = pyrimidine-2-thione or dmpymtH = 4,6-dimethyl-pyrimidine-2-thione) and triphenylphosphine (PPh₃) have been synthesized and structurally characterized. All copper and two of the silver compounds, namely [Cu(PPh₃)₂(pymtH)₂]BF₄ (1), [Cu(PPh₃)₃(pymtH)]BF₄ (2), [Cu(PPh₃)₂(dmpymtH)₂]BF₄ (3), [Cu(PPh₃)₃(dmpymtH)]BF₄ (4), [Ag(PPh₃)₃(pymtH)]NO₃ (5) and [Ag(PPh₃)₃(dmpymtH)]NO₃ (6), reveal a tetrahedral coordination environment while [Ag(PPh₃)₂(pymtH)]NO₃ (7) preferentially adopts a trigonal planar arrangement. The stoichiometry of the isolated silver complexes does not always follow the respective stoichiometries of the synthetic procedures. The photophysical properties of all the isolated products have been evaluated. In solution, phosphine derived emission is detected while in the solid state only [Cu(PPh₃)₃(dmpymtH)]BF₄ (4) emits from a state of different parentage. All of the complexes were also tested for in vitro antibacterial activity against four bacterial strains and for anti-inflammatory activity by measuring lipoxygenase inhibition activity.