Ti51Ni44Si5 alloy exhibits martensitic transformation, in which the transformation peak temperatures A(superscript *) and M(superscript *) of this alloys are higher than those of equiatomic or Ni-rich TiNi alloys, but lower than those of Ti51Ni49 alloy. There are three different phases in 950℃ annealed Ti51Ni44Si5 alloy, including the gray Ti(Ni,Si) matrix, the black Ti5(Ni,Si)3 particles and the gray χ phase. DTA test results show that the annealed Ti51Ni44Si5 alloy has three endothermic peaks in the thermograph, in which the 1168℃ endothermic peak is associated with the reverse eutectic transition of the Ti5(Ni,Si)3 phase accompanied with the local Ti(Ni,Si) matrix molten around the Ti(Ni,Si) grain boundaries, the 1270℃ endothermic peak is associated with the reverse peritectic transformation of χ-phase→Ti(Ni,Si)+Liq. and the one at 1293℃ is the dissolution reaction of Ti(Ni,Si)→Liquid.