Isolation of phenols from the middle oil fraction(170-230°C) of tar produced in the multi-cogeneration system has been investigated for the purpose of recovering valuable pure phenols, such as phenol, cresols, xylenol and ethyl-phenol. Phenolic compounds were separated from the middle oil by liquid-liquid extraction using alkali and sulfuric acid. The yield of phenolic fraction from the middle oil (170-230°C) is up to 37%, which is much higher compared with those of metallurgical coke plants. Chromatography-mass spectrometry was used to analyse phenolic compounds. The result shows that the phenol content is less than 2%, and main compounds are cresol(14%), xylenol(20%) . Phenols of the middle oil fraction(230-280°C) was also analysed, which main contain methyl naphthol(20%).