Vertically-oriented graphene nanowalls (VGNWs) have been successfully synthesized under different experimental conditions (such as flow rate of argon, growth temperature, plasma power as well as deposition time) on copper foils in the reactive methane and argon environment using a capacitively coupled plasma-enhanced horizontal tube furnace deposition system. It is shown that the morphology and structure of VGNWs can be effectively tailored by experimental conditions. Furthermore, the growth mechanism of VGNWs produced in the plasma-based approach has been investigated. The synthesized VGNWs are used as anode materials in Li-ion batteries and the batteries show outstanding cycle efficiency (~99%). The specific capacity of coin-type cells can be improved by adjusting the experimental parameters and reaches 400 mAh g−1 in the first charge-discharge cycle. This work is particularly important for the development of an advanced process for the synthesis and application of carbon-based nanomaterials.