133 Cs NMR is a valuable tool for non-invasively probing biological systems. As a congener of potassium, it accumulates in the intracellular space, primarily through the action of the Na þ -K þ pump (ATPase). In addition, it is possible to resolve the MR signal of 133 Cs in different tissue compartments on the basis of chemical shift or MR relaxation properties. This compartmental resolution applies not only to the intra-and extracellular spaces, but to subcellular compartments as well. In this review, we discuss the studies defining the ion transport, chemical shift and relaxation characteristics of 133 Cs in living systems. We also review the application of 133 Cs NMR to evaluation of ion transport across membranes and the kinetic/ chemical environment of the intracellular space in systems ranging from red blood cells to rat brain.