Five new complexes based on 1-phenyl-1H-tetrazole-5-thiol (Hptt): 1,1′-diphenyl-5,5′- dithiodi-tetrazole (abbreviated as dptt) (1), {[Co2(OH)2(2,2′-bipy)2(Hptt)2]·(ptt)2·(H2O)2}(2), [Cd2I2(2,2′-bipy)2(ptt)2] (3), [Co(ptt)2]n (4) and [Cd(ptt)2]n (5), have been synthesized and fully characterized by elemental analyses, thermogravimetric analysis, powder X-ray diffraction, IR spectra and single-crystal X-ray diffraction. Structural analysis indicated that compound 1 is an organic matter generated from in situ oxidative coupling reaction of Hptt ligands under the help of Fe3+ ion. In compound 2, two Hptt ligands adopting μ2-κN, κS bridging mode and two μ2-OH¯ bridge two Co(2,2′-bipy) fragments into a[Co2(OH)2(2,2′-bipy)2(Hptt)2]2+ core with short Co⋯Co distance (2.8185(10) Å). In compound 3, two Cd centers are joined into a dinuclear complex with short Cd⋯Cd distance (3.9282(14) Å) by two ptt¯ anions in μ2-κS, κS bridging mode. Compounds 4 and 5 are isostructural and both feature one-dimensional (1D) looped chain structures containing 8-membered [M2S2C2N2] rings (M = Co for 4, M = Cd for 5). Variable-temperature magnetic susceptibility measurement of compounds 2 and 4 reveal strong antiferromagnetic interactions between Co centers. The fluorescent properties of compounds 1, 3 and 5 are investigated in the solid state.