The utilization of bioactive compounds from fresh produce waste, which is gaining attention in the agri-food and cosmetics industries, focuses on employing green extraction over conventional extraction methods. This emerging field addresses environmental concerns about food waste and the uses of bioactive phytochemicals for skin health. Modern green extraction methods aim to minimize the energy-intensive process and the use of harmful solvents. These techniques include ultrasound, microwave, and supercritical fluid extraction, pulsed electric field extraction, pressurized liquid extraction, and subcritical water extraction methods, which provide high efficacy in recovering bioactive phytochemicals from vegetable and root crops. The phytochemicals, such as carotenoids, polyphenols, glucosinolates, and betalains of fresh produce waste, exhibit various therapeutic properties for applications in skin health. These dietary antioxidants help to neutralize free radicals generated by UV radiation, thus preventing oxidative stress, DNA damage, and inflammation. The skin care formulations with these phytochemicals can serve as natural alternatives to synthetic antioxidants that may have toxic and carcinogenic effects. Therefore, this review aims to discuss different green extraction technologies, consumer-friendly solvents, and the beneficial skin health properties of selected phytochemicals. The review highlights recent research on major phytochemicals extracted from vegetables and root crops in relation to skin health.