In this work, a ZnO nanowires/graphene nanohybrid was synthesized by a three steps approach. Copper substrates were covered with graphene by chemical vapor deposition, further ZnO nanowires were electrochemically deposited on the as grown graphene on copper and finally a transfer process was employed for moving the heterostructure onto a different substrate. A comprehensive structural analysis which included scanning electron microscopy, X-ray diffraction and Raman measurements revealed that the ZnO nanowires crystallize in wurtzite structure perpendicular to graphene, the process leading to the formation of a nanohybrid heterostructure. The band gap energy of the ZnO nanowires deposited on graphene was estimated to be 3.11 eV, as calculated from the reflectance spectrum analysis. The GGA-PBE+U within Grimme (DFT-D) approach was used to provide an accurate description of the interface structure in terms of electronic and optical properties, confirming that the decrease in the band gap energy of ZnO nanowires is caused by the interaction with the graphene surface. The findings of this study could serve as an experimental and theoretical reference for upcoming studies on ZnO NWs/Graphene nanohybrid-based optoelectronic applications.