•SFE as a green alternative to conventional extraction of bioactive compounds.•Techniques and methodologies for SFE improvement.•Experimental design for optimization of SFE operational conditions.•Structural characterization of bioactive compounds obtained by SFE. An ideal extraction method should be swift, yield quantitative recovery without degradation, and the extracts should be easily separated from the solvent. The development and application of alternative green technology to replace conventional extraction methods with improved extraction efficiency and low environmental impact for the determination of natural bioactive compounds is therefore, highly important. Supercritical fluid technology offers features that overcome many limitations of conventional extraction methods. This review presents an analytical overview regarding the application of supercritical fluids in the extraction of bioactive compounds and their operative extraction conditions, along with the investigation of further improvements on the extraction efficiency and the applied techniques for the structural characterization and identification of such bioactive compounds.