In this work, we report development of hybrid nanostructures of metal nanoparticles (NP) and carbon nanostructures with strong potential for catalysis, sensing, and energy applications. First, the etched silicon wafer substrates were passivated for subsequent electrochemical (EC) processing through grafting of nitro phenyl groups using para-nitrobenzene diazonium (PNBT). The X-ray photoelectron spectroscope (XPS) and atomic force microscope (AFM) studies confirmed presence of few layers. Cobalt-based nanoparticles were produced over dip or spin coated Nafion films under different EC reduction conditions, namely CoSO₄ salt concentration (0.1 M, 1 mM), reduction time (5, 20 s), and indirect or direct EC reduction route. Extensive AFM examination revealed NP formation with different attributes (size, distribution) depending on electrochemistry conditions. While relatively large NP with >100 nm size and bimodal distribution were obtained after 20 s EC reduction in H₃BO₃ following Co²⁺ ion uptake, ultrafine NP (<10 nm) could be produced from EC reduction in CoSO₄ and H₃BO₃ mixed solution with some tendency to form oxides. Different carbon nanostructures including few-walled or multiwalled carbon nanotubes (CNT) and carbon nanosheets were grown in a C₂H₂/NH₃ plasma using the plasma-enhanced chemical vapor deposition technique. The devised processing routes enable size controlled synthesis of cobalt nanoparticles and metal/carbon hybrid nanostructures with unique microstructural features.