Two new bioactive silver–organic frameworks [Ag(μ3-PTAS)]n(NO3)n·nH2O (1) and [Ag4(μ4-PTAS)(μ5-PTAS)(μ2-SO4)2(H2O)2]n·2nH2O (2) were easily assembled, thus opening up the application of PTAS as a versatile N,S-building block in the crystal engineering of MOFs. The obtained products reveal infinite 3D networks driven by multiply bridging PTAS spacers that adopt unprecedented N2S-coordination modes. The topological analysis of 1 discloses an uninodal 3-connected net with the srs (SrSi2) topology, whereas 2 features a pentanodal 3,4,5-connected net with a hitherto undocumented topology. Apart from representing the first MOFs derived from PTAS, the compounds 1 and 2 display notable antibacterial and antifungal activities.