Low-pressure chemical vapor deposition (LP-CVD) technique has been utilized for controlled growth of carbon nanotube (CNT) arrays on silicon wafers. The tube-diameters of CNTs and the number of graphene layers are controlled by varying the thickness of catalyst films. The catalyst particle density and the growth conditions such as the ambient gas and the local environment are all crucial for the formation of vertically aligned CNT arrays. The length of CNT arrays can be controlled by altering the growth time. In addition, the supercapacitive properties of CNT arrays with various morphologies growing on different current collectors have been investigated using a less corrosive 0.5 M Na2SO4 aqueous solution as the electrolyte. Vertically aligned CNT arrays on Ti-Si substrate produce a higher capacitance compared to randomly oriented CNTs on the same current collector. Furthermore, Ni foam enables better utilization of active materials than Ti-Si substrate. CNT arrays electrodes fabricated by this simple, low cost approach demonstrate stable and consistent capacitor behaviors for a wide range of scan rates. Moreover, CNT arrays electrodes provide better platform for further integration with transitional metal oxide, via simple sputtering or electrodeposition technique, to enhance the supercapacitive performance.