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After diffusion processing of thermal spraying aluminum on 20# steel is discussed in this article.Variations of microstructure, composition as well as microhardness and corrosion resistance of diffusion layer of spray aluminum are explored by means of X-ray diffraction, scan electron microscopy (SEM) as well as electron probe microanalysis (EPMA).The result shows that diffusion layer of spray aluminum consists ofη phase (Fe2Al5) ,ζ phase (FeAl2) ,β2 phase (FeA1), β1 phase (Fe3Al) and αphase from surface to substrate.There are balanced transitions between phases.The layer has extra high hardness and corrosion resistance.