Grape marc seeds contain large amounts of different polyphenolic compounds so they can be used for the recovery of these classes of compounds. A new green extraction method for the recovery of phenols from the grape seeds was developed. To provide a high quality extract sourced from natural product by using enzymes as alternative solvents and spending less energy, it is impeccable to call this method “green”. Furthermore, this method was optimized by finding out which conditions provide the best possible results and achieving the maximum recovery of polyphenols from grape seeds. The optimization of the enzyme-assisted extraction of phenols was conducted using the commercially available oenological enzyme preparations with respect to the enzyme dosage, temperature, extraction time, pH value and enzyme preparation by applying the response surface methodology. Optimal conditions were determined using the enzyme preparation Lallzyme EX-V, at the extraction temperature of 48 °C, extraction time of 2 h and 43 min, pH 3.5 and enzyme dosage of 20.00 mg g−1. The new optimized extraction method is less expensive, simple, fast, precise and selective for the recovery of simple phenols (monomeric and dimeric form) and since it is based on the environmentally friendly extraction solvent it may provide a valuable alternative to the conventional extraction methods. The obtained extracts can be used for the application in pharmaceutical, food and cosmetic industry.