Efficient thermal energy storage technologies based on phase change materials (PCMs) that are capable of reversibly harvesting tremendous thermal energy during the isothermal phase transition have recently received unprecedented attention and are booming explosively in the exploitation of state-of-the-art multifunctional composite PCMs. In this regard, the smart integration of versatile metal oxides into PCMs has made significant contributions. However, a comprehensive review associated with the smart utilization of multifunctional metal oxides in PCMs is lacking. Here, we systematically summarize recent advances concerning the smart utilization of multifunctional metal oxides in PCMs for thermal storage, thermal transfer, energy conversion, and advanced versatile applications. This review aims to provide in-depth insights into the interactive relationships between multifunctional metal oxides and PCMs, thus providing a guide for the target design of high-performance multifunctional composite PCMs. We also highlight the current challenges and possible future research directions.