Abstract: A total of 30 ambient air samples was collected from 6 cities in Anhui Province using 2,4-dinitrophenylhydrazine (DNPH) sampling tubes with reference to HJ 683-2014. The sampling tube was eluted with 5 mL of acetonitrile, and the eluent was collected, diluted to 5 mL with acetonitrile, filtered with 0.45 μm needle filter, and analyzed by high performance liquid chromatography. Agilent EC-C₁₈ column with packing particle size of 2.7 μm was used as the stationary phase, and mixed solution composed of acetonitrile and water at various volume ratios was used as the mobile phase for gradient elution. The targets separated were detected by diode array detector at the detection wavelength of 360 nm. It was shown that derivatives of the 13 aldehydes and ketones (formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, methacrolein, butanone, butyraldehyde, benzaldehyde, valeraldehyde, m-tolualdehyde and n-hexaldehyde) could be separated within 14 min, and linear relationships between values of mass concentration (calculated by aldehydes and ketones) and peak area of the 13 targets were kept in the range of 0.1-2.0 mg·L^-1, with detection limits (3.143s) of 0.11-0.37 μg·m^-3. Test for precision on the mixed standard solution of aldehydes and ketones derivatives was made, and RSDs of the determined values (n=6) was 0.080%-1.6%. Test for recovery was made in the blank sampling tube, with detection amounts of formaldehyde, acetaldehyde and acetone in the blank sampling tube of 0.055, 0.035, 0.080 μg, and recoveries of the 13 targets in the range of 84.1%-108%. The proposed method was applied to the analysis of the 30 actual samples, and formaldehyde, acetaldehyde, acetone, butanone and butyraldehyde were all detected in the ambient air of the 6 cities. The detection amount of butyraldehyde was the highest, the detection amounts of propionaldehyde, methacrolein, benzaldehyde, m-tolualdehyde, n-hexaldehyde and acrolein were lower, and crotonaldehyde and valeraldehyde were not detected. The total detection amounts of the 13 targets in 30 samples were 16.78-44.53 μg·m^-3.