The structural characterization of three compounds of a mixture of taxoids from the Taxus wallichiana was achieved by employing the combinations of two-dimensional 1 H–1 H COSY, 1 H–13C HMQC, 1 H–13C HMBC and LC–MS techniques. In the mixture of taxoids, 13-acetyl-13-decinnamoyltaxchinin (3) showed some specific ROE correlations, which were found to be different from earlier reports for a similar molecule. Besides complementing the NMR results, LC–MS data also indicated the presence of three compounds.