Three novel bioactive silver–organic networks, namely, the 2D polymer Ag­(μ3-PTA)­(chc) n ·n(Hchc)·2nH2O (1), the 3D bioMOF Ag2(μ3-PTA)2(μ2-chdc) n ·5nH2O (2), and the 2D polymer Ag2(μ2-PTA)2(μ4-H2chtc) n ·6nH2O (3), were constructed from 1,3,5-triaza-7-phosphaadamantane (PTA) and various flexible cyclohexanecarboxylic acids as building blocks {cyclohexanecarboxylic (Hchc), 1,4-cyclohexanedicarboxylic (H2chdc), and 1,2,4,5-cyclohexanetetracarboxylic (H4chtc) acid, respectively}. The obtained products 1–3 were fully characterized by IR and NMR spectroscopy, ESI-MS(±) spectrometry, elemental and thermogravimetric (TGA) analyses, and single-crystal and powder X-ray diffraction. Their structural diversity originates from distinct coordination modes of cyclohexanecarboxylate moieties as well as from the presence of unconventional N,N,P-tridentate or N,P-bidentate PTA spacers. Topological classification of underlying metal–organic networks was performed, disclosing the hcb, 4,4L28, and a rare fsc-3,4-Pbcn-3 topology in 1, 2, and 3, respectively. Moreover, combination of aqueous solubility (S 25°C ≈ 4–6 mg mL–1), air stability, and appropriate coordination environments around silver centers favors a release of bioactive Ag+ ions by 1–3, which thus act as potent antibacterial and antifungal agents against Gram-positive (S. aureus) and Gram-negative (E. coli and P. aeruginosa) bacteria as well as a yeast (C. albicans). The best normalized minimum inhibitory concentrations (normalized MIC) of 10–18 (for bacterial strains) or 57 nmol mL–1 (for a yeast strain) were achieved. Detailed ESI-MS studies were performed, confirming the relative stability of 1–3 in solution and giving additional insight on the self-assembly formation of polycarboxylate Ag–PTA derivatives and their crystal growth process.