Carbon dioxide in its liquid or supercritical state (scCO(2)) has a prodigious potential as an environmentally benign reaction medium for sustainable chemical synthesis. Since the mid-1990s, rapidly increasing research efforts have shown that scCO(2) can replace conventional and potentially hazardous solvents in a wide range of processes. There is also increasing evidence that the application of scCO(2) can broaden the scope of catalytic synthetic methodologies. On the basis of the experience in our laboratories, this report analyzes the impact of scCO(2) on green organometallic catalysis.