Aldehydes and ketones (AKs) in cigarette smoke are risk to humans and environment. Due to the complexity of itself and the interference of the smoke tar matrix, the aldehydes and ketones in particle phase (AKPs) of mainstream smoke (MSS) and sidestream smoke (SSS) have not been well investigated. In this study, the AKPs of MSS and SSS were derivatized into polar products by reaction with Girard T reagent. The derivatives were isolated rapidly by column chromatography and analysed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Fifteen species of aldehydes and ketones were detected by positive ion electrospray ionization (ESI) FT-ICR MS: O1–6, N1O1–4, N2O1–3 and N3O2–3. The total number of AKPs obtained by ESI FT-ICR MS in MSS and SSS is about 1100 and 970, respectively. After hydrolysis, the original AKPs were obtained and 63 carbonyls were identified and quantified by gas chromatography–mass spectrometry (GCMS). The nitrogen-containing and high-oxygen AKPs were further characterized by Orbitrap mass spectrometry. Structures of compounds with high relative abundance in the mass spectrum were speculated (e.g. a series of degradants of cembrenediol) by comparison with the results of GCMS.