Cloud point extraction (CPE), a promising and simple technique for the separation of organic compounds using surfactants (Genapol X-080 [oligoethylene glycol monoalkyl ether] and PEG 8000 [polyethylene glycol with molecular weight of 8000]), was used to recover polyphenols from wine sludge (wine production waste). The effect of various parameters such as surfactant concentration, temperature, and pH on the percentage of phenol recovery and phase volume ratio during phenol separation from wine sludge was investigated, and the derived optimum parameters were used as the basis for the selection of CPE conditions. When a two-step CPE with a total of 4% v/v of Genapol X-080 (pH = 3.5, temperature = 55 °C, and time = 30 min) or 10% v/v of PEG 8000 (pH = 2.5, temperature = 55 °C, and time = 30 min) was applied the phenol recovery values achieved were 75.8 or 98.5%, respectively. Phenols recovered from wine sludge using the above surfactants maintained high antiradical activity as determined by the 1,1-diphenyl-2-picrylhydrazyl method.