Wood-related procedures, such as lumberjacking and pruning, inevitably result in big piles of leaves, which are considered a major by-product. Extracting valuable compounds from natural by-products is an ongoing trend. In this work, the use of Pulsed Electric Field (PEF) was evaluated as a pretreatment step, prior to the ultrasound-assisted extraction of phenolic compounds from Aesculus carnea leaves. In addition, various solvent systems were examined, as well as the time of pretreatment with PEF. According to the results, up to 33% more phenolic compounds can be extracted, under optimum conditions (30% ethanol in water as solvent and PEF pretreatment for 30 min, compared to the same solvent, without PEF). Moreover, PEF treatment time was not (i.e., 30 and 60 min) and no differences were recorded, suggesting that a lower treatment time can yield the same extraction of phenolic compounds. As such, the use of PEF is highly recommended in combination with ultrasound extraction, to maximize the yield of phenolic compounds extracted from the leaves of Aesculus carnea.