Gold(I) and silver(I) complexes of 1-methyl-5-thio-tetrazole (1) have been prepared and the coordination chemistry of this ligand toward metal-phosphine frameworks has been explored. As indicated by IR and Raman data, ligand 1 is deprotonated and the resulted anion acts as a bidentate (S,N)-tetrazole-5-thiolato unit in the new gold(I) complexes, [Au(SCN4Me)(PPh3)] (2), [{Au(SCN4Me)}(2)(mu-dppm)] (3), and [{Au(SCN4Me)}(2)(mu-dppe)] (4), while it is coordinated only through the sulfur atom as its neutral tetrazole-5-thione form in the silver(I) derivative, [Ag(HSCN4Me)(PPh3)](2)(OTf)(2) (5). Further characterization of the new compounds was performed using multinuclear (H-1, C-13, P-31, F-19) NMR spectroscopy, mass spectrometry, and DSC measurements. Single-crystal X-ray diffraction studies revealed basically linear P-M-S arrangements in complexes 3-5. The bidentate (S,N) coordination pattern results in a T-shaped (S,N)PAu core in 3 and 4, whereas, in 5, a similar coordination geometry is achieved in the dimer association based on S-bridging ligand 1. Herein, weak (C)H center dot center dot center dot Au and (C)H center dot center dot center dot Ag agostic interactions were observed. An intramolecular Au center dot center dot center dot Au contact occurs in 3, while in 4 intermolecular aurophilic bonds lead to formation of a chain polymer. An intermolecular Ag center dot center dot center dot Ag contact is also present in the dimer unit of 5. Low-temperature P-31 NMR data for 5 evidenced the presence of monomer and dimer units in solution. Theoretical calculations on model of the complexes 2 and 4 are consistent with the geometries found by X-ray diffraction studies.