Abstract The conformational behavior of citral was examined by NMR spectroscopy and DFT calculations wherein s - trans conformations were found to dominate over s - cis conformations based on temperature-dependent vicinal and through-space couplings and the calculations. The amount of s - cis conformation present, however, is non-negligible. The coupling constants were also calculated with a good correlation with the experiments, with an exception that too low a value for vicinal coupling of the s - trans conformer of the conjugated CH–CH O system was predicted. According to DFT, the most stable structure is an E - s - trans conformer which is 2.0 kJ mol −1 more stable than the most stable Z - s - trans conformer, i.e. E -citral is slightly more stable than Z -citral.