First representatives of Ag(I) scorpionates bearing tris(2-pyridyl)phosphine oxide (Py3P[dbnd]O), viz. [Ag(Py3P[dbnd]O)(PPh3)]BF4 (1) and [Ag(Py3P[dbnd]O)(PPh3)]ClO4 (2), have been synthesized and structurally characterized. X-ray diffraction analysis reveals that the silver atom of 1 is coordinated by Py3P[dbnd]O and Ph3P ligands in N,N′,N″-tripodal and P-monodentate fashions, respectively. The both complexes exhibit significant cytotoxic activity (IC50 being from 11 to 14 μM) screened in vitro against human larynx carcinoma (Hep-2) cell lines. The luminescent proprieties of the prepared scorpionates are also discussed.