This review provides a comprehensive overview of dibenzyltoluene (DBT)-based liquid organic hydrogen carrier (LOHC) systems, a promising technology for the safe, efficient, and scalable storage and transportation of hydrogen. Owing to their high thermal and chemical stability, low toxicity, and compatibility with existing energy infrastructure, DBT and its fully hydrogenated form (H₁₈-DBT) are among the most advanced candidates for industrial LOHC applications. Despite these advantages, several technical challenges remain, including high dehydrogenation temperatures (>300 °C), catalyst deactivation (coke formation and sintering), and slow molecular diffusion within porous supports. Recent progress in catalyst design — particularly through the development of bimetallic catalysts (e.g., Pd–Ni) and nanostructured supports — has significantly improved reaction efficiency and cycle stability. In addition, the integration of thermo-electrochemical hybrid approaches and process intensification strategies offers further potential for enhancing system performance. This review critically assesses the current state of DBT-based LOHC systems, highlights ongoing advancements, and identifies future research directions needed to overcome existing limitations and enable the commercial-scale deployment of this technology within a sustainable hydrogen economy.