Semiconductor heterostructure composite materials, exemplified by p-n junctions, have garnered substantial interest for their elevated ionic conductivity, crucial in solid oxide fuel cells (SOFCs). The inherent built-in electric field (BIEF) within these materials enhances ion transport while hindering electron flow, thereby mitigating the risk of short circuits. This research focuses on the electronic conduction properties of p-n junctions, specifically through the development of high-performance LiCo0.5Al0.5O2 (LCAO)-Ce0.8Sm0.2O2-δ (SDC) semiconductor heterojunction composite electrolytes for low-temperature solid oxide fuel cells (LT-SOFCs). Experimental results demonstrate a correlation between the electrolyte's performance and the LCAO to SDC weight ratio. The SOFC equipped with a 3LCAO-7SDC electrolyte achieved an open-circuit voltage (OCV) of 1.1 V and a maximum power density (MPD) of 1013 mW/cm2 at 550 °C, significantly outperforming other composite ratios and single-phase SDC electrolytes, which only reached 453 mW/cm2 under identical conditions. High-resolution transmission electron microscopy (HRTEM) revealed the presence of non-uniform interfaces within these composites. Energy band structure analyses confirm superior ionic conductivity and effective charge separation capabilities. This study introduces a novel p-n junction design for LT-SOFC electrolyte materials using LCAO-SDC, further advancing the exploration of p-n junctions in this application.