Successful growth of vertically aligned carbon nanotube (CNT) arrays on copper substrate by thermal chemical vapor deposition is reported in this paper. The effects of Ti, Ni, and Ni-Cr intermediate layers have been studied to eliminate cracking of the copper surface during the synthesis of CNTs. It was found that these intermediate layers play a critical role in achieving vertical alignment of CNTs on copper substrates. The effects of other reaction parameters such as flow rate of ethylene, concentration of water vapor, and deposition temperature have also been studied. Scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy were used to evaluate the quality and nature of the CNT formed.