Liquid phase catalytic exchange (LPCE) appears a highly promising technology for separating hydrogen isotopes due to being less energy-intensive and having a high separation factor. This paper provides an overview of the current development of the hydrophobic catalysts used in the LPCE process, including the LPCE fundamentals, factors influencing its effectiveness, and proposals for future research areas. This paper specifically reviews the active metal catalysts, catalyst supports, operating temperatures, and molar feed ratio(gas-to-liquid,G/L). The addition of a second metal such as Ir, Fe, Ru, Ni, or Cr and modified catalyst supports showed enhancement of LPCE performance. Additionally, the validated optimized temperature of 60–80 °C and G/L of 1.5–2.5 provide an important basis for designing LPCE systems to improve separation efficiency. This paper concludes by highlighting potential research areas and challenges for future advancements in the sustainability of LPCE for hydrogen isotope separation, which include the optimization, scalability, techno-economic analysis, and life-cycle analysis of modified catalyst materials.