As the global demand for sustainable and renewable resources intensifies, there is an imperative to explore innovative technologies for biomass valorization. This review delves into a promising avenue, providing an overview of green approaches that combine solid-liquid extraction (SLE) with a type of solvent known as deep eutectic solvents (DESs) in a synergistic manner. SLE, a conventional method for isolating bioactive compounds from biomass, is recognized for its effectiveness in sample preparation. However, it often involves the use of environmentally harmful solvents. Subsequently, DESs have emerged as an eco-friendly alternative to traditional solvents. Composed of naturally occurring and benign components, these DESs exhibit unique properties that render them suitable for various extraction processes. The integration of SLE with DESs introduces a novel approach to biomass valorization. This review explores the synergistic effects between SLE and DESs to optimize extraction yields, improve selectivity, and reduce overall energy consumption. Furthermore, the nature of DESs aligns with the principles of green chemistry, positioning them as a sustainable alternative to traditional solvents.