Zn-doped TiO2 nanofibers shelled with ZnO hierarchical nanoarchitectures have been fabricated combining electrospinning of TiO2 (anatase) nanofibers and metal-organic chemical vapor deposition (MOCVD) of ZnO. The proposed hybrid approach has proven suitable for tailoring both the morphology of the ZnO external shell as well as the crystal structure of the Zn-doped TiO2 core. It has been found that the Zn dopant is incorporated in calcined electrospun nanofibers without any evidence of ZnO aggregates. Effects of different Zn doping levels of Zn-doped TiO2 fibers have been scrutinized and morphological, structural, physico-chemical and optical properties evaluated before and after the hierarchical growth of the external ZnO shell over the electrospun nanofibers. Moreover, doping promotes the incipient transition from the anatase to rutile phase in the core-shell Zn-doped TiO2-ZnO nanostructures at lower temperature than that observed for pure TiO2. Finally, the present core-shell hierarchical nanofibers possess a very large surface to volume ratio and exhibit a marked cathodoluminescence with a strong UV and visible emission.