Significant advances in the solubilisation of both hydrophilic and lipophilic molecules in near-critical fluids, particularly CO2, have recently been achieved. These developments have emerged through the design and synthesis of CO2 compatible amphiphiles, including surfactants for water-in-CO2 microemulsions and larger block copolymers which form micelles and stabilise emulsions in CO2, Novel derivatised dendrimers with a polar core have also been utilised for the solubilisation of polar molecules in CO2.