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This study is an investigation of a hybrid hierarchical electrode produced by electrospinning and chemical vapor deposition methods. The binderless hybrid hierarchical electrode is composed by carbon nanofibers with carbon nanotubes inside and outside the fibers. Single- walled or multi-walled carbon nanotubes are present inside the nanofiber as a dopant and they are incorporated during the carbon nanofiber electrospun production. After that, multiwalled carbon nanotubes are grown onto the surface of the carbon nanofiber using chemical vapor deposition method.