Ionic conduction in perovskite oxide is commonly tailored by element doping in lattices to create charge carriers, while few studies have been focused on ionic conduction enhancement through tailoring microstructures. In this work, remarkable enhancement of ionic conduction in titanate has been achieved via in situ growing active nickel nanoparticles on an oxide surface by controlling the oxide material nonstoichiometry. The combined use of XRD, SEM, XPS and EDS indicates that the exsolution/dissolution of the nickel nanoparticles is completely reversible in redox cycles. With the synergetic effect of enhanced ionic conduction of titanate and the presence of catalytic active Ni nanocatalysts, significant improvement of electrocatalytic performances of the titanate cathode is demonstrated. A current density of 0.3 A cm-2 with a Faradic efficiency of 90% has been achieved for direct carbon dioxide electrolysis in a 2 mm-thick YSZ-supported solid oxide electrolyzer with the modified titanate cathode at 2 V and 1073 K.