In white wine production, the technique consisting of freezing whole or crushed grapes usually increases the levels of aroma-related compounds in the final wine products. However, this technique may affect phenolic compounds, among other chemical compounds. Phenolic compounds are crucial to white wines because of their susceptibility to oxidation and their role with regard to color stability. In this study, white wines made from Muscat of Alexandria grapes were subjected to two different freezing techniques: whole-bunch freezing and crushed-grape freezing. In addition, a pre-fermentative maceration was applied to each experiment in order to determine if the effects of freezing were comparable to those of maceration. The phenolic compounds studied were gallic acid, protocatechuic acid, caffeic acid,trans-coutaric acid, and epicatechin, which are the key compounds from the point of view of wine stability. The freezing of crushed grapes enhanced the extraction of phenolic compounds in comparison to the freezing of whole bunches of grapes without pre-fermentative maceration. On the other hand, the effect of pre-fermentative maceration was comparable to that resulting from freezing crushed grapes. This step made the must from whole frozen grapes having even larger levels of phenolic compounds. Without pre-fermentative maceration, freezing whole bunches of grapes only allowed a moderate extraction of phenolic compounds and produced wines with lower individual phenolic contents than those obtained through traditional winemaking procedures.