Thermal insulation material (TIM) is a vital component of Marine Reefer Container (MRC)’s enclosure structure. Facing with industry development and innovation as well as social low-carbon requirements, MRCs urgently need optimization and improvement of TIMs. According to current research, application status and special marine environment, the primary TIMs of MRC are summarized. Comparison and properties introduction were made. The TIM development trend was also proposed. The polyurethane foam material composited with vacuum insulation panel (VIP) was highlighted and scientifically analyzed. Tiny-closed-cell is the developing and innovation direction of Polyurethane. The polyurethane + vacuum insulation panels’ collaborative multi-layer insulation structure is currently the most efficient enclosure structure. The reasonable internal insulation layer layout of VIPs is an ideal design, but further optimization is needed by theoretical simulation and experimental research. This work aims to provide a reference for the choice and design optimization of TIMs for MRCs.