The aim of this paper is to study how grape ripeness and ethanol concentration affect the extraction of color and phenolic compounds from skins and seeds during the maceration/fermentation process. Simulated maceration assays were carried out with the grapes at three stages of berry development (vitis vinifera cv. Tempranillo) and different percentages of ethanol in the maceration media. Both ripeness and ethanol content have a considerable effect on the extraction of color and phenolic compounds. Of these two factors, ripeness increases the extractability most. The presence of ethanol in the medium facilitates anthocyanin and especially proanthocyanidin extraction, but it also decreases copigmentation phenomena, which can decrease the color intensity. The higher the ethanol concentration is in the maceration media, the higher the astringency of proanthocyanidins.