The flexible linear multidentate ligands 1,5-bis(8-quinolylsulfanyl)-3-oxapentane (OESQ) and 1,8-bis(8-quinolylsulfanyl)- 3,6-dioxaoctane (ODSQ) reacted with silverperchlorate affording the simple mononuclear complexes [Ag(OESQ)]ClO4 1 and [Ag(ODSQ)]ClO4 2, respectively. However, with silver nitrate, novel metallosupramolecular complexes [Ag4(ODSQ)2(η1-NO3)2(η2-NO3)2] 3 and [Ag4(OESQ)(ODSQ)(η1-NO3)2(η2-NO3)2] H2O 4 were obtained, in which the co-ordination motifs [Ag(OESQ)] and [Ag(ODSQ)] are spontaneously self-assembled by sulfurbridged silver ions into tetrametallotricyclic molecules containing the same or mixed building blocks. All four complexes have been characterized by elemental analyses, IR and 1H NMR spectroscopy, and single crystal X-ray diffraction methods. The possible self-assembly process has been discussed with the aid of electrospray mass spectrometry.