A new flower-like hybrid structure consisting of nitrogen-doped 3-dimensional (3D) graphene and vertically aligned graphene has been synthesized using a combination of low-pressure chemical vapor deposition (LPCVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques. Active nitrogen (N) species were found to be essential for the growth of the flower-like morphology. N-doping was responsible for enhanced electrical conductivity and wettability of the obtained nano-carbon hybrid structure. Based on the conducted studies a growth mechanism has been proposed. The high specific surface area, low resistance to charge transfer and enhanced specific capacitance of this nitrogen-doped hybrid structure, makes it an excellent candidate material for supercapacitors.