Effect of water mist on the small-scale solid fuel polyvinyl chloride (PVC) fire in the confined space has been studied experimentally with the heat release rate measured by a cone calorimeter in this paper. The water mist is generated by a single pressure nozzle and the diffusion flame is produced from PVC samples respectively. The LDV/APV system is employed to determine the water mist characteristics. The Cone Calorimeter is used to measure the heat release rate, oxygen and carbon monoxide concentrations and other important parameters of the interaction under various conditions. The results of the test showed that heat extraction cooling (flame cooling and fuel surface cooling) plays a dominating role to suppress the PVC fire, when the water mist with enough volume flux are applied to the diffusion flame in the confined space. The higher the operation pressure, the easier the suppression. The faster the PVC fire suppressed by water mist with large enough water flux, the less the total amount of toxic gases (CO, CO2) produced.