This article reports a number of functional 3D networks based on the coordination bonds between the silver(l) ion and polycyclic aromatic 2,3,6,7,10,11 -hexakis(organylthio)triphenylene (HRTT) molecules. First, 2,3,6,7,10,1 1 -hexakis(phenylthio)triphenylene (HPhTT) chelates with AgBF4 (or AgTf, where Tf is triflate) in the presence of hexafluorobenzene to form a 3D network (composition, HPhTT center dot AgBF4; space group, I (4) over bar), where each Ag(l) atom is bonded to three HPhTT molecules and acts as a three-connected node that interconnects the trigonal HPhTT ligands. In addition to the relatively rare 8(2)center dot 10-a topology, the network features distinct channel-like domains that incorporate various solvent molecules (e.g., acetone and tetrahydrofuran). The solvent molecules can be evacuated to produce a stable and crystalline apohost network, in which the solvent-accessible fraction of the cell volume is calculated to be about 16%. Second, chelation of 2,3,6,7,10,11 -hexakis(4-methoxyphenylthio)triphenylene (HMOPhTT) and AgSbF6 in a 1:1 ratio results in a 3D network featuring a similar 8(2)center dot 10-a topology and Ag(l) coordination environment. However, the crystallographic symmetry (space group Cc) is lowered, and the feature of porosity is much less distinct. The 3D networks show strong room-temperature fluorescence bands with lambda(F,max) = 450 nm, due to the pi-electron fragment of the tripherylene group.