Considered esoteric only a few years ago, research into the stable isotope geochemistry of transition metals is moving into the geoscience mainstream. Although initial attention focused on the potential use of some of these nontraditional isotope systems as biosignatures, they are now emerging as powerful paleoceanographic proxies. In particular, the Fe and Mo isotope systems are providing information about changes in oxygenation and metal cycling in ancient oceans. Zn, Cu, Tl, and a number of other metals and metalloids also show promise. Here we review the basis of stable isotope fractionation as it applies to these elements, analytical considerations, and the current status and future prospects of this rapidly developing research area.