The synthesis and characterization of the silver(I) chloride complex of formula{[AgCI(CMBZT)(TPTP)2]⋅(MeOH)}(1) (CMBZT = 5-chloro-2-mercaptobenzothiazole, TPTP = tris(p-tolyl)phosphine) is described. Also the structure of the hydrate derivative{[AgCI(TPTP)3]⋅(0.5⋅H2O)}(2) of the corresponding known anhydrous silver complex (Zartilas et al., 2009), and the polymorph3of the known[AgI(TPTP)3]complex (Zartilas et al., 2009) were determined and compared with the known ones. In addition, the structure of the known one silver(I) cluster{[AgI(TPTP)]4}(4) (Meijboom et al., 2009) was re-determined at 120(2) K and possible Ag-Ag interactions were analyzed. The compounds1–4were characterized by X-ray crystallography at r.t (1) and 120 K (2–4). All these complexes and{[(Et3NH)+]2⋅[Ag6(μ3-Hmna)4(μ3-mna)2]2−⋅(DMSO)2⋅(H2O)}(5) (Hmna = 2-mercaptonicotinic acid) were evaluated for cytotoxic and anti-inflammatory activity. Thein vitrotesting of cytotoxic activity of1–5against leiomyosarcoma cancer cells (LMS), were evaluated with Trypan Blue and Thiazolyl Blue Tetrazolium Bromide or 3-(4.5-dimethylthiazol-2-yl)-2.5-diphenyltetrazolium bromide (MTT) assays. The flow cytometry assay for complex1and showed that at 15 μMof1, 62.38% of LMS cells undergo apoptosis, while 7% of LMS cells undergo cell necrosis. The antitumor activity of3is comparable with that of its reported polymorph (Zartilas et al., 2009). The anti-inflammatory, activity of complexes1–3and5was also studied. The activity towards cell viability was2>3>5>1>4, while the order of the inhibitory activity in cell growth proliferation follows the order,2>3>1>4>5. The anti-inflammatory activity on the other hand is1>2>5>⋯>3.