Vertically aligned carbon nanofibers (VACNFs) were grown by plasma-enhanced chemical vapor deposition (PECVD) using Ni nanoparticle (NP) catalysts that were deposited by airbrushing onto Si, Al, Cu, and Ti substrates. Airbrushing is a simple method for depositing catalyst NPs over large areas that is compatible with roll-to-roll processing. The distribution and morphology of VACNFs are affected by the airbrushing parameters and the composition of the metal foil. Highly concentrated Ni NPs in heptane give more uniform distributions than pentane and hexanes, resulting in more uniform coverage of VACNFs. For VACNF growth on metal foils, Si micropowder was added as a precursor for Si-enriched coatings formed in situ on the VACNFs that impart mechanical rigidity. Interactions between the catalyst NPs and the metal substrates impart control over the VACNF morphology. Growth of carbon nanostructures on Cu is particularly noteworthy because the miscibility of Ni with Cu poses challenges for VACNF growth, and carbon nanostructures anchored to Cu substrates are desired as anode materials for Li-ion batteries and for thermal interface materials.