The CaNb2O6 and ZnNb2O6 columbites (Sp.gr. Pbcn) were studied as oxygen ion conductors both theoretically and experimentally. A theoretical approach included geometrical-topological analysis, bond valence site energy (BVSE) and density functional theory (DFT) calculations. The BVSE approach showed the possibility of pure oxygen ions diffusion with migration energies less than 0.45 eV in both compounds. However, DFT calculations indicated the possibility of diffusion of both anions and cations. The single-phases columbites were synthesized by the Pechini method for accurately determine charge carriers type and investigated by impedance spectroscopy, by the Tubandt method, which confirmed the absence of cationic conductivity, and measured the electrical conductivity as a function of oxygen partial pressures. The CaNb2O6 sample was characterized by the pure oxygen-ionic conductivity ∼2 × 10−6 S cm–1 at 800 °C (E a = 0.82 eV), while the ZnNb2O6 had a similar conductivity value due to mixed ionic-electronic contribution (E a = 0.83 eV). The electromotive force method also showed the predominance of the ionic type of conductivity in CaNb2O6, while ZnNb2O6 has a mixed conductivity with ion transport number of about 0.4. Additionally, we synthesized Ti-doped samples MNb2−x Ti x O6–0.5x (M = Mg, Ca; x = 0.1, 0.2) to study the doping effect on conducting properties.