We illustrate a novel concept in tailoring the architecture of MOF-derived carbons by doping MOF crystals with transition metal ions prior to carbon structure growth via chemical vapor deposition (CVD). MOF-5 was isomorphously doped with various concentrations of Ni²⁺ during synthesis and was subsequently subjected to CVD to grow a labyrinth of carbon nanofibers (CNF) with high electrical conductivity and higher surface area than that of the parent MOF. TEM of the inner structure of the CNFs revealed a chevron arrangement with ~0.34 nm visible fringe spacing. The CNF diameters increased with increasing Ni concentration. This is attributed to the decreasing distance between Ni dopants with increasing Ni concentration, which may facilitate coalescence of the Ni catalyst during the heat treatment and thereby increase the diameter of the resultant CNF. However, Ni doping concentration greater than 30% led to large agglomerations of Ni particles which eventually ceased CNF growth. The electrical conductivity and the electrochemical double layer capacitance of the CNFs also increased with increasing Ni concentrations. The highest electrochemical double layer capacitance and the lowest resistance was observed at a Ni doping concentration of 30%. An alkaline electrolyte was used to engage the Ni particles inside the CNFs to participate in a reversible redox reaction shuttling between Ni and Ni(OH)₂, which resulted in a specific capacitance as high as 349 F/g. The possibility of doping transition metals into a wide variety of MOF structures can provide a new method to synthesize novel carbon structures with high energy storage capabilities.