Using of clean technology media such as SCFs in chemical processes has attracted increasing attention. So far in the light of promising results gained from extraction, material synthesis and reactions in SCFs, there is no doubt in its obvious place in green chemistry. In this field, designing molecules that are soluble in scCO2 is a challenging goal. Amongst several different methods to overcome poor solubility of some molecules in scCO2, attachment of CO2-philic ponytails has been a successful option. The objective of this research was to synthesize new families of scCO2-philic ligands based on PDMS derivatives. A series of new PDMS ligands and their metal complexes were prepared and screened during the C-C coupling reactions in scCO2.It includes a brief review of research directed towards extractions, materials synthesis and reactions in liquid and scCO2.The information in this book will help shed some light on this new and challenging alternative reaction medium for synthetic organic chemistry. This book should be especially useful to professionals and graduate students in Green Chemical Technologies.