A molecularly imprinted polymer (MIP) was prepared using 2,4-dimethylphenol (2,4-DMP) as template. The synthesis is optimized by using three different porogens, chloroform, acetonitrile and toluene. The MIP was used as a class-selective sorbent in molecularly imprinted solid-phase extraction (MIP-SPE) for pre-concentration and determination of phenolic compounds from the environmental water. The difference in recognition selectivity of the polymer columns was observed in HPLC system. The variables affecting the extraction efficiency of MIP-SPE procedure were systematically investigated to facilitate the class-selective extraction of phenols from spiked water samples. The spiked aqueous solution was adjusted to pH 6.0 before being percolated through the MIP-SPE cartridge at the flow rate of 0.5 mL min−1. After rinsing with dichloromethane, the bound phenolic compounds were desorbed with acetonitrile containing 5% aqueous ammonia. The developed MIP-SPE method was demonstrated to be applicable to the analysis of phenolic compounds in the environmental water.