A method for the extraction, separation, fractionation and purification of biopolymers from plant materials using supercritical and/or subcritical solvent extractions is disclosed. Specifically, the process can be used for the separation of resins and rubber from guayule shrub (Parthenium argentatum), and other rubber and/or resin containing plant materials, using supercritical solvent extraction, for example supercritical carbon dioxide extraction. Additionally, polar and/or non-polar co-solvents can be used with supercritical carbon dioxide to enhance the selective extraction of resins and rubbers from the shrub.