The growth and electron emission characteristics were investigated from a hybrid structure of multiwalled carbon nanotubes (MWCNTs) and multilayer layer graphene (MLG) deposited on silicon substrate coated with iron catalyst and an interlayer of aluminium. The hybrid structures were synthesized in a two-step process by microwave plasma-enhanced chemical vapour deposition technique. The formation of MWCNTs takes place by absorption and precipitation of carbon radicals into the catalyst particles. Thereafter, ample carbon forms MLG on tip of the MWCNTs resulting in a MLG-MWCNTs hybrid nanostructure. MLG was observed to grow branching out of the tips and sidewalls of the MWCNTs and is expected to attach by Van der Walls bonds. Transmission electron microscopy and micro-Raman spectroscopy confirmed the crystalline nature of the hybrid structures. Electron emission studies were carried out using a diode-type field emission setup. The enhancement factor was found to be *3,500 for bare MWCNTs, *4,070 to *5,000 for hybrid structures and *6,500 for N-doped MLG-MWCNTs hybrid structures. Modification in the defects structure and enhancement of emission sites are suggested to be responsible for the increase of the field emission characteristics.