Rosemary solid distillation waste (SWR), a by-product of the essential oil industry, represents an important source of phenolic antioxidants. Green technologies such as ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE), and accelerated solvent extraction (ASE) of phenolic compounds from SWR were optimized as valorization routes to maximize yield, rosmarinic acid (RMA), carnosol (CARO) and carnosic acid (CARA) contents. Response surface methodology was used in this context, with ethanol concentration (X1), extraction temperature (X2), and time (X3) being the independent variables. A second-order polynomial model was fitted to the data, and multiple regression analysis and analysis of variance were used to determine model fitness and optimal conditions. Ethanol concentration was the most influential extraction parameter, affecting phenolic compounds, while the influence of other parameters was moderate. The optimized conditions were as follows: X1: 67.4, 80.0, and 59.0%, X2: 70, 51, and 125 °C, and X3: 15, 10, and 7 min for MAE, UAE, and ASE, respectively. A comparison of optimized MAE, UAE, and ASE with conventional Soxhlet extraction techniques indicated that ASE provided a higher extraction yield and content of phenolic compounds. However, UAE represented the best process from an environmental point of view, allowing an improved extraction of phenolics from SWR with high energy efficiency and low energy costs.