The effects of micro‐mixer pattern, volumetric flow ratio, capillary length, inner diameter of capillary, residence time, and phenol concentration on phenol microfluidic extraction were investigated. The results indicated that the extraction performances of phenol with Y‐shape joint were higher than that with T‐shape joint. The smaller inner diameter of capillary could improve extraction performances of phenol. The phenol concentration of the inlet in aqueous phase had slight influence on phenol microfluidic extraction. The inner diameter of capillary of 1.0 mm, volumetric flow ratio of 1:1, capillary length of 2 m, and residence time of 88.3 s were more suitable for extraction of phenol. The overall volumetric mass transfer coefficient of phenol reached 0.0036 s−1 at residence time of 8.8 s. The extraction efficiency of phenol realized 99% at residence time of 23.6 s. The extraction of phenol from aqueous solution depended on intermolecular forces and hydrogen bonds between MIBK and phenol.