Two kinds of Fe-based amorphous coatings were fabricated by detonation spray at various oxygen fuel ratios and spray distances. The microstructure and amorphous content of as-sprayed coatings were characterized. The hardness, wear properties and wear mechanisms of coatings on the substrate of stainless steel were investigated. Results show that the Fe-based amorphous coatings having a high hardness and a low wear rate can be obtained by increasing the amorphous phase and decreasing the porosity of coating. The wear mechanism of coating depends significantly on the amorphous content and porosity. Adhesive wear dominates the wear process when the amorphous content of coating is less than 81.32%. However, the fatigue wear becomes the dominative mechanism of wear when the amorphous content is higher than 84.35%, meanwhile, the high porosity (≥2.1%) leads to a serious fatigue wear. Oxidation wear occurs during all the friction process, especially the serious oxidation would happen with the increase in content of metals such as Fe, Cr and Mo in Fe-based amorphous coatings.