Oxime-derived palladacycles are very efficient and versatile pre-catalysts for a wide range of carbon–carbon bond coupling reactions in air, under very low loading conditions, and employing reagent-grade chemicals. This tutorial review presents the main achievements, advantages and limitations of oxime palladacycles as a source of highly active palladium nanoparticles for high-turnover catalyzed Heck, as well as other homo- and cross-coupling reactions usually carried out employing organic or aqueous solvents. Comparison with other ligandless Pd(II) catalysts is also presented. Recent advances to develop supported oxime-derived palladacycles in order to facilitate precatalyst recovery and reuse in cross-coupling reactions, especially under aqueous reaction conditions, are also discussed.