AbstractPulsed gradient spin echo NMR is a powerful technique for measuring diffusion coefficients. When coupled with appropriate data processing schemes, the technique becomes an exceptionally valuable tool for mixture analysis, the separation of which is based on the molecular size. Extremely fine differentiation may be possible in the diffusion dimension but only with high‐quality data. For fully resolved resonances, components with diffusion coefficients that differ by less than 2% may be distinguished in mixtures. For highly overlapped resonances, the resolved spectra of pure components with diffusion coefficients that differ by less than 30% may be obtained. In order to achieve the best possible data quality one must be aware of the primary sources of artifacts and incorporate the necessary means to alleviate them. The origin of these artifacts are described, along with the methods necessary to observe them. Practical solutions are presented. Examples are shown that demonstrate the effects of the artifacts on the acquired data set. Many mixture analysis problems may be addressed with conventional high resolution pulsed field gradient probe technology delivering less than 0.5 T m−1(50 G cm−1). © 2002 Wiley Periodicals, Inc. Concepts Magn Reson 14: 225–258, 2002.