Liquid chemical spills that occur on land could lead to serious safety issues. A kind of confinement material consisted of phenolic foam with good fire resistance and chemical resistance was put forward. A barrier (65 cm-wide, 26 cm-high) was constructed by phenolic foam. According to the water-resistance and oil-resistance experiments, we found that the barrier could block the spill movement completely. Mixed liquid of gasoline and ethylene glycol was chosen as the experimental fuel. The barrier remained its form under fire (maximum temperature > 850°C) for 30 min. The temperature inside the barrier was below 60°C, which showed the good heat insulation. Under fire condition for 30 min, part of the barrier became carbonization but not be burned. The flame border on the top of the barrier reached 41 cm away from the fire side of the barrier. In the whole process, the experimental fuel was stopped in one side of the barrier. In addition, some key factors to assess this confinement technology were put forwarded. Hence, as the confinement barrier, the use of phenolic foam provided a rapid and efficient approach for stopping the liquid chemical spills and flowing fires.