An analytical method to quantify particulate-phase high molecular weight mono-carbonyls (C# > 5) and di-carbonyls has been developed by adopting 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by high performance liquid chromatography/ultra-violet (HPLC/UV) detection. Satisfactory reproducibility and precision of the measurements were achieved. This method was applied to measure the carbonyls in PM2.5 collected on quartz-fiber filters, sampled in Xi’an, China, from 2008 to 2009. Nonanaldehyde was the most abundant compound, followed by octanaldehyde, hexanaldehyde and heptaldehyde, accounting for 40%, 20%, 12% and 11% in the total quantified carbonyls. For dicarbonyls, the concentration of methylglyoxal was much higher than that of glyoxal. The seasonal variations of the particulate-phase mono-carbonyls and dicarbonyls were similar to those in the gas-phase, namely winter > autumn > spring > summer (except octanaldehyde). A strong correlation among those carbonyls was observed in winter, resulting from low temperature partitioning, weaker photochemical reaction, and more primary emission sources. In contrast, in summer, vehicle emissions, cooking emissions and photochemical reactions are the major pollution source in Xi’an.