Highly purified 5-vinyl-1H-tetrazole was synthesized, which is in great demand in modern medicine and industry as a monomer for obtaining nitrogen-rich macromolecular compounds and a reagent for the complete synthesis of biological compounds. The molecular structure was studied experimentally with sequential X-ray diffraction analysis and theoretically with ab initio quantum chemical calculations. The data from differential scanning calorimetry, nuclear magnetic resonance (1H, 13C, 1H-15N, HMBC), high-resolution mass spectrometry and vibrational spectroscopy were analyzed. The results are useful for evaluating the possibility of extending the polymerization of 5-vinyl-1H-tetrazole to synthesize polymers with predictable molecular weight and thermodynamic parameters.