Using Ce LIII edge X-ray absorption near edge spectroscopy (XANES), it is shown that acceptor dopants introduced to cerium members of the rare earth ortho-niobate series, Ce1-xSrxNbO4±δ and Ce1-xCaxNbO4±δ, are charge compensated by the formation of holes on the cerium sublattice. These spectroscopic studies are complemented by structural studies, using X-ray and neutron powder diffraction, determining that the solubility limit of the strontium and calcium dopants within the CeNbO4+δ structure is ~10% and ~30% respectively. Under oxidising conditions, the Ce3+/Ce4+ redox couple facilitates reversible redox processes, and it is observed that the Ce1-xSrxNbO4±δ and Ce1-xCaxNbO4±δ materials form commensurate and incommensurately modulated oxygen hyperstoichiometric phases as a function of temperature. Under reducing atmospheres, this redox activity is suppressed, and charge-compensating Ce4+ holes are annihilated.