Polyurethane/melamine phosphate composite foam (MP-PUF) was prepared from poly(adipate)diol/melamine phosphate composite (f=2), polyether-polyol (f=4.6), and PMDI (f=2.5). The thermal properties of MP-PUF such as morphology, closed-cell content, thermal conductivity, and thermal stabilities were characterized. Water was used as a blowing agent, and the composition of melamine phosphate (MP) was maintained at $1.43{pm}0.3wt%$ of MP-PUF. As the content of water increased, the thermal conductivity of pure polyurethane foam (PUF) decreased, whereas the thermal conductivity of MP-PUF increased. The thermal stabilities of the PUF and the MP-PUF were maximized at 5 php $H_2O$, and then decreased at the higher $H_2O$ contents. The thermal stabilities of MP-PUF were greatly enhanced due to the synergetic effect of MP and urea, which was generated during the blowing process. The temperature of 50% residual mass of MP-PUF increased to $370{sim}450^{circ}C$ and the temperature of 30% residual mass exceeded over $700^{circ}C$. Compared to the PUF, the temperature of 50% residual mass and 30% residual mass were higher than 25 and $70^{circ}C$, respectively.