NMR spectral analysis of saccharides is often hampered by the narrow range of 1 H chemical shifts, resulting in substantial multiplet overlap and rampant strong coupling situations. We chose the tetrasaccharide stachyose (Gal1(a1®6)Gal2(a1®6)Glc3(a1®2b)Fru4) as a representative example. Within the all-12 C isotopomer, the H2[ 12 C] and H3[ 12 C] protons of the Gal1 unit are strongly coupled (Dn !", = ca. 18 Hz, 3 JH2H3 = 10.3 Hz). Their multiplets also overlap, as is the most easily observed from the 13 C-decoupled HSQC spectrum (Figure ), making it impossible to invert just one of them using a Ws-selective pulse in SERF or PSYCHEDELIC experiments. Within the 13 C2 or 13 C3 isotopomers, the H2[ 13 C a ] and H3[ 13 The strong coupling between H2[ 12 C] and H3[ 12 C] in Gal1 also affects the accuracy of coupling measurements to other protons. This is illustrated by comparing the 3 JH1H2 measurement in Gal1 and Gal2. In contrast to Gal1, H2[ 12 C] and H3[ 12 C] in Gal2 are better separated (Dn !", = ca. 45 Hz). Figure shows a pure shifted TSE-PSYCHEDELIC experiment with the Ws-frequency selective pulse set to the anomeric H1[ 12 C] protons of both Gal1 and Gal2 in order to measure 3 JH1H2 on the H2[ 12 C] signals. The two obtained splittings differ by a small yet significant amount of 0.3 Hz. When ignorant of the effects of strong coupling, one may be deceived and conclude a small difference in ring conformation between both galactose units. The real reason is that the strong coupling between H2 and H3 in Gal1 causes the H1-H2 splitting to fall somewhere in-between the actual 3 JH1H2 and the 4 JH1H3 values (the latter being close to zero). The same coupling measurement using the H2[ 13 C a ] signals in SERFBIRD (Figure ) does so under a weak coupling condition for both galactose units, yielding accurate and identical 3 JH1H2 values. Focusing on 13 C isotopomers comes with the additional advantage that we can make good use of the 13 C chemical shift to mitigate 1 H spectral overlap when even pure shift resolution turns out insufficient. An example is shown in Figure , where a SERFBIRD experiment is used to measure the 3 JHH coupling between the Glc3 H5 and H6b protons that are strongly coupled in the all-12 C isotopomer. Because H6b is part of a methylene group, its response is suppressed in SERFBIRD and only the H5[ 13 C b ] signal is visible. The H5[ 13 C b ] pure shift signal turns out overlapped with Fru4 H4[ 13 C b ], and since the Glc3 H5-H6b coupling is small, the doublet in F1 is not cleanly resolved. Since the Glc3 13 C5 and Fru4 13 C4 chemical shifts are separated by 2.7 ppm (405 Hz), co-sampling a small amount (k = 0.025) of 13 C chemical shift evolution in t1 provides an elegant route to disentangle these signals (Figure ). In this way, the two proton responses are effectively separated by ca. 10 Hz along the F1dimension. Using SERFBIRD, nearly all vicinal 1 H-1 H couplings in stachyose could be readily extracted. The only exceptions were vicinal couplings involving the geminal proton pair H6a and H6b in Gal1, which are very strongly coupled. As both protons simultaneously experience a 1 JCH coupling in the 13 C6 isotopomer, their strong coupling cannot be circumvented in this way. For the same reason, the geminal coupling between them could not be measured, as well as between the chemical shift degenerate Fru4 H1a-H1b protons. For measurement of the geminal Gal2 H6a-H6b and Fru4 H6a-H6b couplings, the chemical shifts of both protons were sufficiently different so that PSYCHEDELIC could be used. Measurement of the geminal Glc3 H6a-H6b coupling was complicated by strong coupling between H6b and H5. The H6b 13 C satellites can be used to avoid this, but as SERFBIRD cannot observe protons with geminal coupling partners, SATASERF had to be used instead (Figure ). An overview of all extracted couplings is provided in the supporting information, with comparison to couplings extracted using PSYCHEDELIC where possible (Table ).