The NMR of oriented molecules gives detailed structural information, but isotopic substitution is often required for analysis. An alternative to synthesizing labeled molecules is to observe multiple-quantum spectra. Symmetry arguments show that multiple-quantum transitions yield similar information and that the spectra can be predicted by analogy with labeling experiments. Several examples are shown to illustrate the versatility of this technique for determining molecular conformations and rates of intramolecular processes. © 1981, American Chemical Society. All rights reserved.