The stabilization of red wine color by the copigmentation phenomenon is a crucial process that does not always proceed favorably under natural conditions during the first stages of vinification. The impact of the prefermentative cold maceration technique on the phenolic composition and magnitude of the copigmentation level of organic Tempranillo wines elaborated in a warm climate have been studied as an enological alternative to the traditional maceration for obtaining highly colored wines. Tristimulus colorimetry was applied to study the color of wines during vinification, and a high-performance liquid chromatography (HPLC) procedure was used for the analysis of phenolic compounds. Spectrophotometric and colorimetric analyses were also performed to evaluate the copigmentation level of the wines. Significant chemical and color differences were found depending on the maceration technique applied. Prefermentative cold macerated wines were richer in those compounds accounting directly for the color of red wine (anthocyanins) and those involved in anthocyanin stabilization through copigmentation reactions (phenols), which was in accordance with the higher copigmentation degree and darker, more saturated and vivid bluish colors. The evaluation of the copigmentation based on colorimetric parameters in the CIELAB color space showed that prefermentative cold maceration caused greater effectiveness of copigmentation than traditional maceration since it induces more important and hence more easily perceptible color changes.