The 1H nuclear magnetic resonance spectra of phenylpropynal and 1-phenylpropyne are analyzed for CS2/C6D12 and acetone-d6 solutions. The ensuing spin–spin coupling constants over eight formal bonds are used in assessing the conformational dependence of the one in the propynal derivative, as compared to the one over six bonds in benzaldehyde. The eight-bond coupling constant in phenylpropynal implies, via a hindered rotor model, that the twofold barrier to internal rotation is 5.9 ± 1.6 kJ/mol in both solutions. This number is much smaller than that for the internal barrier in benzaldehyde, reflecting the reduced π electron conjugation in phenylpropynal. Molecular orbital computations, with geometry optimization, confirm the essentially purely twofold internal barrier in the free propynal. The theoretical magnitudes are given for AM1 calculations, as well as for abinitio computations with STO-3G, 3-21G, 6-31G, and 6-31G* bases. To within experimental error, the barrier magnitudes from the split-valence basis sets agree with those obtained in solution.