Synthesis of well-defined, surface-initiated poly(N-octyl-p-benzamide) brushes was demonstrated using a new "grafting from" chain growth technique. A solution-based chain growth polycondensation technique was adopted from literature and modified to form a polyaramid brush by taking advantage of the differences in substituent effects between the activated surface-grafted initiator (methyl 4-(methyl(3-(trimethoxysilyl)propyl)carbamoyl)benzoate) and the deactivated deprotonated monomer (methyl 4-(octylamino)benzoate). The surface-immobilized polymer brushes on silicon wafers were characterized using ellipsometry, goniometry, grazing-angle attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. In addition, polyaramid brushes were grown from high surface area Stober silica and studied using thermogravimetric analysis, and the degrafted polymers were characterized using gel permeation chromatography and nuclear magnetic resonance spectroscopy. This is believed to be the first report of polyaramid brushes prepared by the surface-initiated chain growth polymerization technique, and the overall method allows for the preparation of novel aromatic polymer brush structures that could not be previously synthesized.