Facile synthesis method of undoped and rare earth metals (REM) doped (RE = Yb, Eu and Eu:Yb) one-dimensional ZnO nanostructures with high REM concentration using electrospinning followed by calcination at 500 °C were carried out. One-dimensional (1D) ceramic nanostructures were characterized in terms of morphology, structure, and optical properties. The analysis carried out revealed highly crystalline nature of ZnO wurtzite structure and hybrid nanofibers with a mixture of crystalline phases. High-resolution X-Ray Photon Spectroscopy spectra confirmed successful Eu and Yb modification of ZnO lattice revealing the existence of Eu2+, Eu3+ and Yb3+ ions. The optical properties results showed reduction in optical energy band gap from 3.02 eV to 2.55 eV for undoped and Eu:Yb doped ZnO 1D nanostructures, respectively. The influence of Eu, Yb, and Eu:Yb codoping on ZnO electrospun nanostructures was investigated, and potential application of such obtained nanofibers was proposed as photon upconversion material for photocatalysis.