Lanthanum silicate oxyapatites with and without calcium (Ca) and iron (Fe) doping, La10Si5FeO26.5 (LSFO) and La9.5Ca0.5Si5.5Fe0.5O26.5 (LCSFO), are synthesized by sal-gel process (SGP) and solid state reaction process (SSP). The phase formation, microstructure and conductivities of LSFO and LCSFO oxyapatites are characterized by X-ray diffraction (XRD), scanning electron spectroscopy (SEM) and complex impedance analysis. The morphologies of LCSFO oxyapatite nanoparticles synthesized by SGP were characterized by transmission electron microscope (TEM). The thermal and decomposition properties of the LCSFO gel were analyzed by simultaneous differential scanning calorimetry and thermal gravimetric analysis (DSC-TGA). The results show that the phase formation of LCSFO synthesized by SGP occurs at temperatures as low as 750 degrees C, significantly lower than similar to 1500 degrees C required for LCSFO synthesized by SSP. Co-doping of Ca and Fe significantly improves the densification, sinterability and oxide-ion conductivity of lanthanum silicate oxyapatites. The best results were obtained on LCSFO synthesized by SGP, achieving oxide-ion conductivity of 2.08 x 10(-2) S cm(-1) at 800 degrees C, which is higher than 5.68 x 10(-3) S cm(-1) and 1.04 x 10(-2) S cm(-1) for LSFO and LCSFO synthesized by SSP, respectively, under the identical test conditions. (C) 2015 Elsevier B.V. All rights reserved.