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The undercooling of Ni-W-P ternary alloy coating melt was investigated by in situ differential scanning calorimeter (DSC) with the flux processing technique. The results showed that the highest undercooling of Ni-W-P ternary alloy with 359 K was obtained as the thermal treatment temperature of the melt being 1679 K and the cooling rate being 50 K min −1 . When cooling rate is fixed, the change of undercooling depends on the melt processing temperature, and the undercooling will increase rapidly at the first stage. The effects of thermal treatment temperature and cooling rates on the undercooling were discussed.