Sol-gel capillary microextraction (CME) is a new direction in the solventless sample preparation for the preconcentration of trace analytes, and presents significant interest in environmental, pharmaceutical, petrochemical, biomedical, agricultural, food, flavor, and a host of other important areas. It utilizes advanced material properties of organic-inorganic hybrid sol-gel polymers to perform efficient extraction and preconcentration of target compounds from a wide variety of matrices. In the present work, a novel benzyl-terminated dendron-based sol-gel coating was developed for CME. A detailed investigation was conducted to evaluate the performance of the newly developed sol-gel dendrimer coatings to perform solventless extraction of a wide range of polar and nonpolar analytes. The characteristic branched architecture of dendrons makes them structurally superior extraction media compared with their traditional linear polymeric counterparts. Sol-gel chemistry was used to chemically immobilize dendritic macromolecules on fused silica capillary inner surface. Due to the strong chemical bonding with the capillary inner walls, sol-gel dendron coatings showed excellent thermal and solvent stability in capillary microextraction in hyphenation with chromatographic analysis. Efficient extraction of a wide range of analytes from their aqueous solutions was accomplished using sol-gel dendron coated fused silica capillaries. Low parts per trillion level detection limits were achieved in CME-GC for both polar and nonpolar analytes including polyaromatic hydrocarbons (PAHs), aldehydes, ketones, phenols, and alcohols.