Systemic investigations are performed to comprehend the structural, optical, and electrical characteristics of four niobium (Nb) doped β-Ga2O3 crystals (β-Ga2O3:Nb) grown by the optical floating zone (OFZ) method. All of the β-Ga2O3:Nb crystals revealed monoclinic phases and good crystalline qualities. While the different Nb doped (i.e., 0.0001 mol%, 0.01 mol%, 0.1 mol% and 0.5 mol%) samples exhibited slightly changed bandgap energies Eg (≡ 4.72 eV, 4.73 eV, 4.81 eV, 4.68 eV)—the luminescence features indicated distinctive defect levels—affecting the electronic energy structure significantly. By increasing the Nb doping level from 0.0001 mol% to 0.1 mol%, the Fermi level (EF) moves closer to the bottom of the conduction band. For the sample with Nb doping 0.5 mol%—no further improvement is noticed in the electronic properties. Finally, the energy band diagrams of four samples are given.