Two highly polar sol-gel coatings were developed for capillary microextraction (CME). One of the coatings contained cyanopropyl-polydimethylsiloxane (CN-PDMS) and the other low molecular weight polyethylene glycol. These highly polar coatings were immobilized via sol-gel chemistry allowing for direct chemical bonding to the inner surface of fused silica capillaries. These sol-gel coated microextraction capillaries were employed in CME for solvent-free microextraction and preconcentration of trace analytes (polar, moderately polar, and nonpolar) from aqueous matrices. CN-PDMS and short chain PEG extraction phases exhibit both polar and polarizable characteristics. Therefore, both sol-gel CN-PDMS and short chain sol-gel PEG coatings were able to extract analytes of different polarity from aqueous media. Both sol-gel CN-PDMS and sol-gel PEG coatings provided effective extraction of polar analytes such as free fatty acids, alcohols, and phenols without requiring derivatization, pH adjustment or salting out procedures commonly used in SPME experiments with conventional coatings. For each of these coatings, detection limits on the order of nanogram/liter (ng/L) were achieved for both polar and nonpolar analytes extracted simultaneously from aqueous media followed by GC-FID analysis. Both sol-gel CN-PDMS and short chain sol-gel PEG coated microextraction capillaries showed excellent run-to-run and capillary-to-capillary extraction reproducibility (GC peak area RSD < 6% & 5%, respectively) for nonpolar as well as polar analytes. For the sol-gel CN-PDMS coatings, the upper allowable conditioning temperatures were 330°C and 350°C, for the extraction of polar and nonpolar organic analytes, respectively. Similarly, the sol-gel PEG coatings used for the extraction of polar organic analytes survived a conditioning temperature of 340°C. Both sol-gel CN-PDMS and sol-gel PEG coated microextraction capillaries showed no significant changes in the peak areas of the extracted analytes even after being washed with organic solvents (dichloromethane and methanol (1:1), v/v) for 24 hours. The excellent thermal and solvent stabilities can be attributed to the presence of chemical bonds between the sol-gel coatings and the fused silica surface.