Dual-ion electrolytes with oxygen ion and proton-conducting properties are among the innovative solid oxide electrolytes, which exhibit a low Ohmic resistance at temperatures below 550 °C. BaCo0.4Fe0.4Zr0.1Y0.1O3-δ with a perovskite-phase cathode has demonstrated efficient triple-charge conduction (H+/O2-/e-) in a high-performance low-temperature solid oxide fuel cell (LT-SOFC). Here, we designed another type of triple-charge conducting perovskite oxide based on Ba0.5Sr0.5Co0.1Fe0.7Zr0.1Y0.1O3-δ (BSCFZY), which formed a heterostructure with ionic conductor Ca0.04Ce0.80Sm0.16O2-δ (SCDC), showing both a high ionic conductivity of 0.22 S cm-1 and an excellent power output of 900 mW cm-2 in a hybrid-ion LT-SOFC. In addition to demonstrating that a heterostructure BSCFZY-SCDC can be a good functional electrolyte, the existence of hybrid H+/O2- conducting species in BSCFZY-SCDC was confirmed. The heterointerface formation between BSCFZY and SCDC can be explained by energy band alignment, which was verified through UV-vis spectroscopy and UV photoelectron spectroscopy (UPS). The interface may help in providing a pathway to enhance the ionic conductivities and to avoid short-circuiting. Various characterization techniques are used to probe the electrochemical and physical properties of the material containing dual-ion characteristics. The results indicate that the triple-charge conducting electrolyte is a potential candidate to further reduce the operating temperature of SOFC while simultaneously maintaining high performance.