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Atomic growth process and structure of Amorphous Electroless Coating have beenstudied, using Monte-Carlo simulation method. The simulation results of amorphousNi80P20 coating show that PDFs are in accordance with practical values. The mi-grations of adatoms in coating's growth are different from that of solidification ofamorphous materials. In some cases, the migrated adatoms in the process of growthof amorphous coating are not enough to occupy all vacancies and traps, so the amor-phous coating is micro-porous. The immovable probability k and the largest migrationdistance of adatoms, which lie on the electroless bath components, affect the PDF,volume density and microporosity remarkably.