The extraction of natural products is a critical area of focus in the interdisciplinary domain of applied chemistry, biology, and technology, with an emphasis on the development of eco-friendly and sustainable methodologies driven by increasing consumer demand for environmentally friendly alternatives and industry concerns about sustainable, non-toxic extraction techniques. The yield and composition of natural extracts are contingent upon the extraction method employed and the solvent selected. Emerging technologies are designed to reduce extraction time, increase extraction yield, eliminate the use of solvents, and lessen environmental impact. The pharmaceutical industry has conducted extensive research into the application of innovative extraction technologies, including green technologies. In line with the development of “green technology,” the use of green solvents for the extraction of phytochemicals, as opposed to conventional non-eco-friendly solvents, is of paramount importance. Hydrotropes are one such class of green solvents that enhance the solubility of poorly water-soluble or hydrophobic compounds in aqueous solutions by reducing toxicity, cost-effectiveness, and pH independence. These compounds have the potential to enhance the bioavailability, solubility, dissolution rate, extraction yield, and purity of extracted phytoconstituents. Their use minimizes energy consumption and costs, making them an efficient and sustainable choice in the extraction process. This review highlights the extensive use of hydrotropes in the innovative extraction of phytoactive compounds. It provides a comprehensive overview of hydrotrope chemistry, addresses toxicological concerns, and discusses state-of-the-art extraction technologies. The review also examines factors affecting the yield of phytoconstituents and explores available drug delivery systems. The potential of hydrotropes in this context is promising, paving the way for more efficient and environmentally friendly extraction methodologies.