This Review provides comprehensive guidelines for the design of CO2-philic copolymers through an exhaustive and precise coverage of factors governing the solubility of different classes of polymers. Starting from computational calculations describing the interactions of CO2 with various functionalities, we describe the phase behavior in sc-CO2 of the main families of polymers reported in literature. The self-assembly of amphiphilic copolymers of controlled architecture in supercritical carbon dioxide and their use as stabilizers for water/carbon dioxide emulsions then are covered. The relationships between the structure of such materials and their behavior in solutions and at interfaces are systematically underlined throughout these sections.