Amorphous Ni-P alloy coatings were prepared on 45 carbon steel blocks using electrodeposition method. The thermal effect and quality change of Ni-P alloy coating under heating rate of 20℃/min were analyzed by differential scanning calorimetry (DSC) and thermogravimetry (TG). Coatings were heat-treated at 300℃ and 400℃ for 0, 15, 30, 45, 60, 75min respectively, coating surface was characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), microhardness tester. The result shows that the exothermic peak of Ni-P alloy coating appears at 284.8℃, coating quality and elemental composition are stable during the heat treatment. Crystallization process experiences a transformation of amorphous, metastable state NiP and Ni₅P₂, stable state Ni₃P. The microhardness of coating can be improved remarkably after heat treatment, namely, the maximum value of heat-treated coating is 1036.56HV, which is nearly 2 times as hard as as-deposited coating. The corrosion resistance of heat-treated Ni-P alloy coating in NaCl solution is inferior to as-deposited coating, but they are both much better than 45 carbon steel substrate.