SummaryFast separations of perfluorinated polyethers and polymethylsiloxanes that are composed of 50-80 ohgomers were demonstrated in packed capillary column supercritical fluid chromatography (SFC) using a carbon dioxide mobile phase. Separations were accomplished within 10 min using a 13 cm x 250 I~m i.d. column packed with 2 I~m porous octadecyl bonded silica (ODS) particles. Effects of particle diameter of the packing material and pressure programming on separation were investigated, and packed column SFCwas compared with open tubular column SFC. Results show that as the particle diameter was decreased from 5 to 3 to 2 I~m and the column length was reduced from 85 to 43 to 13 cm, the separation time could be reduced from 70 to 20 to 10 min while still maintaining similar separation (resolution). Short colu mns packed with small porous particles are very suitable for fast SFC separations of polymers.