In this paper,the method of UV-visible reflection spectrum(UV method) was theoretically and experimentally proposed to investigate the initial kinetic characters of the solid-solid reaction with the mixture of dimethylglyoxime and Ni(Ac)_(2)·4H_(2)O,and the mixture of dimethylglyoxime and anhydrous Ni(Ac)_(2) as the modeling reaction examples.The results indicated that the UV method was very sensitive in the initial period of solid-solid reaction.The reactive rates for above two reaction systems were varied non-linearly with the change of reaction time.The fastest reaction rates can be reasonably explained by the formation of the cold-melting layer or cold-dissolvingmelting layer.