Low operating voltage is an important requirement that must be met for industrial adoption of organic field-effect transistors (OFETs). We report here solution fabricated polymer brush gate insulators with good uniformity, low surface roughness and high capacitance. These ultra thin polymer films, synthesized by atom transfer radical polymerization (ATRP), were used to fabricate low voltage OFETs with both evaporated pentacene and solution deposited poly(3-hexylthiophene). The semiconductor-dielectric interfaces in these systems were studied with a variety of methods including scanning force microscopy, grazing incidence X-ray diffraction and neutron reflectometry. These studies highlighted key differences between the surfaces of brush and spun cast polymethyl methacrylate (PMMA) films.