Gold-catalyzed functionalization of semicarbazides (ArNHCONHNH₂) with various terminal alkynes R²C≡CH (R² = Alk or Ar) in the presence of Ph₃PAuNTf₂ (3 mol-%) grants a range of substituted semicarbazones (16 examples; 64–93 %). This novel metal-catalyzed coupling proceeds under mild conditions (PhCl, 60 °C) and demonstrates a high functional group tolerance; the reaction is sensitive to the electronic effects of the substituents in terminal alkynes. Inspection of XRD solid-state structures of three obtained semicarbazones proved their dimerization via weak to moderate strength hydrogen bonding. The structures of the semicarbazones in solutions were studied by concentration dependent ¹H NMR and 2D NMR and these experiments proved the presence of H-bonds between two molecules. The nature and energy of H-bonding (3.8–5.1 kcal/mol), degree of electron density delocalization, and rotational barriers via various bonds in the equilibrium model structures were studied by DFT calculations at the M06-2X/6-311++G** level of theory.