Using a 2-propanol-water (i-PrOH-H₂O) mixture as a host, luminescence and electron paramagnetic resonance (EPR) spectra have been observed for the lowest excited states of the trans and metal-free cis conformers of 2,2‘-bipyridine (bpy), 4-methyl-2,2‘-bipyridine (4-Mebpy), 5-Mebpy, 6-Mebpy, 4,4‘-dimethyl-2,2’-bipyridine (4,4‘-Me₂bpy), 5,5‘-Me₂bpy and 6,6‘-Me₂bpy at 77 K. Both trans and cis conformers are non-fluorescent or very weakly fluorescent for bpy. The trans conformer is non-fluorescent or weakly fluorescent in i-PrOH, while the cis conformer is fluorescent in i-PrOH-H₂O (34 wt% of i-PrOH) for Mebpys and Me₂bpys. The Zn²⁺ complexes with bpy, Mebpys and Me₂bpys are fluorescent. The sublevel kinetics were determined for the lowest excited triplet states of trans-bpy, metal-free cis-bpy, Zn-bpy-(CIO₄)₂, trans-6,6‘-Me₂bpy, metal-free cis-6,6‘-Me₂bpy and Zn-6,6‘-Me₂bpy-(ClO₄)₂ from the analysis of the time-resolved EPR signals at 77 K and optically detected magnetic resonance signals at 1.2 K. The zero field splitting E parameter is determined mainly by the conformation and the effect of coordination to Zn²⁺ is small, while the triplet sublevel kinetics are sensitive to both the conformational change and the metal complex formation with Zn²⁺. The observed anisotropy in the triplet sublevel populating rates of Zn-6,6’-Me₂bpy-(CIO₄)2 is anomalous for a 6,6’-Me₂bpy-localized ³ππ* state.