Carbon nanotube (CNT) forests were grown directly on a silicon substrate using a Fe/Al/Mo stacking layer which functioned as both the catalyst material and subsequently a conductive current collecting layer in pseudocapacitor applications. A vacuum-assisted, in situ electrodeposition process has been used to achieve the three-dimensional functionalization of CNT forests with inserted nickel nanoparticles as pseudocapacitor electrodes. Experimental results have shown the measured specific capacitance of 1.26 F/cm(3), which is 5.7 times higher than pure CNT forest samples, and the oxidized nickel nanoparticle/CNT supercapacitor retained 94.2% of its initial capacitance after 10,000 cyclic voltammetry tests.