A method was developed for the determination of Aroclor 1254 in water samples using polystyrene-divinylbenzene (PS-DVB) solid-phase extraction (SPE) and gas chromatography (GC). The PS-DVB sorbent demonstrated good recoveries of Aroclor 1254 when sulfuric acid (1:1, v:v) was added to the samples. Sample quantification was performed using gas chromatography with a parallel column and dual electron capture detector. Factors in extraction method procedures were optimized, including sample pH, elution solvent, eluting volume and breakthrough volume. With the 1000 ml sample acidified to pH 1.0, a 6.0 ml n-hexane/ethyl acetate (1:1, v:v) elution solvent, and gas chromatographic determination, the recoveries of Aroclor 1254 in spiked water samples ranged from 90.6 to 104%. Across testing days, repeatability ranged from 4.7 to 7.6%. The method detection limit was 0.053 μg/L. PS-DVB exhibited a broader pH stability range, satisfactory recoveries, and good repeatability for Aroclor 1254 extraction. The results indicate that these methods can be used to analyze trace amounts of Aroclor 1254, and represent a new analytical approach for determining polychlorinated biphenyls in water samples.