The dense sintered bodies with >95% theoretical densities were successfully obtained from the $BaZrO_3,;BaCeO_3,;Ba(Zr_{0.7}Ce_{0.3})O_3$ solid solution, and core-shell structured $0.7BaZrO_3-0.3BaCeO_3$ composite powders prepared by sol-gel methods. The activation energy of $Ba(Zr_{0.7}Ce_{0.3})O_3$ solid solution calculated from the Arrhenius plot of the proton conductivities was similar to that of $BaZrO_3$. The activation energy of core-shell structured $0.7BaZrO_3-0.3BaCeO_3$ composite, however, was much lower than that of $BaZrO_3$ or $Ba(Zr_{0.7}Ce_{0.3})O_3$ solid solution, and was very similar to that $BaCeO_3$. These results could be assigned to the Ce-rich grain boundary which was clearly observed by EDX in core-shell structured $0.7BaZrO_3-0.3BaCeO_3$ composite.