The fruit and vegetable business generates millions of tons of residue, which can result in significant economic losses. The increasing global emphasis on sustainable and environmentally friendly technologies has driven interest in the valorization of fruit and vegetable waste (FVW) through the extraction of high-value bioactive compounds. Research suggests that food waste from fruits, vegetables, cereals, and other processing businesses might include bioactive chemicals and nutraceuticals useful for treating various disorders. Various methods have been used to extract secondary metabolites, minerals, and vitamins from food waste. Biosolvents, obtained from renewable sources such as bioethanol, ethyl lactate, and deep eutectic solvents, provide a green alternative to traditional petrochemical solvents, aligned with the ideals of green chemistry and circular economy. This chapter provides a comprehensive review of current biosolvent extraction technologies aimed at efficiently recovering phytochemicals such as polyphenols, flavonoidsFlavonoids, carotenoidsCarotenoids, and essential oilsEssential oils from FVW. Key technologies discussed include microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE), supercritical fluid extraction (SFE), and high hydrostatic pressure (HHP)High hydrostatic pressure (HHP), each enhancing the efficiency of biosolvent-based extractions. It underscores the potential of integrating these green technologies into biorefinery models, promoting sustainable waste management while unlocking economic value from agro-industrial by-products.