Abstract A dispersive liquid–liquid microextraction method (DLLME) combined with high performance liquid chromatography (HPLC) was developed for the extraction and determination of some aldehydes, such as benzaldehyde (BzA), butyraldehyde (BuA) and furfural (Fur) in mainstream cigarette smoke as well as BzA in injectable formulations. After trapping of combustion smoke into sulfuric acid with a laboratory-made smoking machine, aldehydes were converted into their hydrazone derivatives by the reaction with 2,4-dinitrophenylhydrazine (DNPH), and then rapidly extracted by DLLME. The effects of various experimental parameters on the derivatization and extraction were studied and optimized. Under the optimum extraction conditions, linear calibration curves in the range 0.025 to 1.0μg/mL with correlation coefficients of 0.9980–0.9996 were obtained for studied aldehydes. Limit of detections (LODs) for BzA, BuA and Fur were found to be 14.2, 21.3 and 7.92μg/L, respectively. The relative standard deviations (RSDs) for inter–and intra–day assays were lower than 8.50%. Average recoveries for spiked samples were in the range 88.0–109%. The proposed method was successfully applied to the determination of aldehydes in different real samples.