Inverse temperature programming in packed capillary liquid chromatography coupled to evaporative light-scattering detection has been used to resolve native polyethylene glycol (PEG) oligomers. The model compound, PEG 1000, was separated on a 300 mm x 0.32 mm I.D. capillary column packed with 3 microm Hypersil ODS particles with acetonitrile-water (30:70, v/v) as mobile phase. The retention of the PEG oligomers increased with increasing temperature, different from what is commonly observed in liquid chromatography. The retention times of the oligomers were approximately doubled for each 25 degrees C increment of the column temperature in the temperature range 30-80 degrees C. The oligomers were almost unretained and co-eluted at a column temperature of 30 degrees C. At 80 degrees C a baseline separation of more than 22 peaks was obtained, but the last eluting peaks were severely broadened and all oligomers did not elute. When a negatively sloped temperature ramp from 80 to 25 degrees C at -1.5 degrees C/min was applied, the peak shapes were improved, additional peaks were detected and the analysis time was reduced by 48%. In the temperature programming mode, the intra-day precision of the retention times ranged from 0.5 to 5.8% (n=5).