An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C5-C13 hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C5-C13 compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograrns (MID and full scan) could be obtained at the same time. The retension time differences of nC6-nC13 alkanes between GC and TIC were in the range of 0.02-0. 58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C6-C13 hydrocarbon group composition could be used in oil-oil correlation studies.