The green extraction of total phenolic compounds, flavonoids, anthocyanins, and tannins from grape marc was optimized using response surface methodology. The extracts were characterized and analyzed using LC-ESI-QTOF-MS/MS, and free radical scavenging capacity was evaluated. An efficient green extraction method is crucial for improving the recovery rates of these high-value phytochemicals and for sustainably reusing wine by-products. Our study optimized parameters for both conventional and ultrasound-assisted extraction methods, including solution pH, extraction temperature, liquid-to-solvent ratio, and ultrasonic amplitude. The optimized conditions for conventional extraction were identified as 60% ethanol with a pH of 2, a solvent-to-solid ratio of 50:1, extraction time of 16 h at a temperature of 49.2 °C. For ultrasound-assisted extraction, the optimized conditions were determined as 60% ethanol with a pH of 2, a solvent-to-solid ratio of 50:1, and an amplitude of 100% for 5.05 min at a temperature of 60 °C. We also demonstrated that lowering the temperature to 49.5 °C improves the energy efficiency of the extraction process with a minor reduction in recovery rates. Considering all factors, ultrasound-assisted extraction is more suitable for efficiently recovering bioactive compounds from grape marc.