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This paper has studied systematically the preparation technology and its effects on the structure and amorphous forming region (AFR), and theoretical description of the AFR for electroless Ni-P alloys. It has been found that the deposition rates increase and approach a maximum value and then decrease with the increase in the concentration of nickel chloride, sodium hypophosphite and pH value, respectively. However, the deposition rates decrease with the increase in sodium citrate. The AFR is P > 9-10 at.% in the range of concentration of nickel chloride studied. In the ran-e of concentration of sodium hypophosphite studied, there was no crystalline structure observed. The AFR calculated theoretically using the Miedema model was in good agreement with the experimental results. (C) 2002 Elsevier Science B.V. All rights reserved.