The effect of cadmium arachidate (CdA) layers deposited by Langmuir-Blodgett technique on the growth of pentacene thin films and the performance of pentacene-based thin film transistors has been investigated. The hydrophobicity of the SiO2 gate dielectric surface was increased (surface energy reduced) with the deposition of CdA layers as a result of the presence of long hydrophobic alkyl chains attached to the cadmium atoms. The change in surface wetting properties of SiO2 strongly influenced the growth mechanism of pentacene thin films. The grain size and root-mean-square surface roughness of pentacene was decreased with an increase in the number of CdA layers compared to the pentacene deposited on a bare SiO2 surface. Organic thin film transistors (OTFTs) with seven layers of CdA on SiO2 showed the highest mobility of 0.27 cm(2)/Vs and the lowest subthreshold slope of 2.4 V/dec. The enhanced electrical properties of the OTFTs with SiO2/CdA as the dielectric is attributed to the better intermolecular connection, tight packing, and improved surface quality of the pentacene, as evident from the X-ray diffraction (XRD) and atomic force microscopy (AFM) results.