Edible oil extraction is a large and well-developed sector based on solvent assisted extraction using volatile organic compounds such as hexane. The extraction of oil from oilseeds generates large volumes of oilseed by-products rich in proteins, fibres, minerals and secondary metabolites that can be valued. This work reviews the current status and the bio-macro-composition of oilseeds, namely soybean, rapeseed, sunflower and flaxseed, and the refining process, comprising the extraction of oil, the valorisation and separation of valuable secondary metabolites such as phenolic compounds, and the removal of anti-nutritional factors such as glucosinolates, while retaining the protein in the oilseed meal. It also provides an overview of alternative solvents and some of the unconventional processes used as a replacement to the conventional extraction of edible oil, as well as the solvents used for the extraction of secondary metabolites and anti-nutritional factors. These biologically active compounds, including oils, are primordial raw materials for several industries such as food, pharmaceutical or cosmetics.