In order to improve the precision of the detection of volatile phenols in ambient air and enhance the detection efficiency, the chromatographic conditions in the Determination of phenolic compounds in ambient air high performance liquid chromatography: HJ 638—2012 were optimized. In this paper, the column temperature was set at 40 ℃, 70.00% acetonitrile and 30.00% water which containing 0.10% formic acid was used as the initial mobile phase, the flow rate was 1.5 mL/min, the ultraviolet detection wavelength was 280 nm, and the injection volume was 10.0 μL, which achieved rapid and efficient separation of volatile phenolic compounds by high performance liquid chromatography(HPLC), and the method was used for the determination of 11 volatile phenols in ambient air in Beijing. Eleven volatile phenols in the ambient air of Beijing were determined by this method. The results showed that the volatile phenol contents in the range of 1.0 to 100.00 μg/mL had good linear correlation with the correlation coefficients>0.998 0. The method detection limits were all ≤6 492.0 ng/m³ with the relative standard deviations of 2.99% to 8.01% and the recoveries of 96.63% to 126.23% at the sample volume of 72 L. This method is in compliance with the industry requirements. This indicates that the precision and accuracy of the detection method established in this paper are high. In summary, this study presents a more efficient HPLC method with more significant separation effect, and it can meet the needs of monitoring volatile phenols in ambient air and exhaust gases.