Various alkylamines are commonly used for efficient Au recovery; however, their high hydrophilicity can result in dissolution in water, hindering effective Au recovery and potentially causing environmental contamination. Currently, the forms in which alkylamines are immobilized on supports provide unsatisfactory Au recovery capabilities and exhibit low structural stability. This study proposes a pragmatic approach for synthesizing amine-laden polymeric fiber (ALPF) adsorbents with efficient Au recovery capabilities and superior structural stability. Polyacrylonitrile fibers (PANF) were employed as a supportive matrix to immobilize the alkylamine molecules chemically. The densely grafted amine groups on the ALPF adsorbed significant amounts of Au ions and reduced them to Au(0) crystals. This chelation–precipitation hybrid method achieved a Au recovery efficiency of nearly 100 % over a wide pH range of 1–4. In addition, it demonstrated an exceptional Au adsorption capacity of 1463 mg/g, surpassing the values reported for other adsorbents categorized by size and shape. Even in the presence of 14 different coexisting metal ions, the ALPF showed a Au recovery efficiency above 99.9 %. It also exhibited excellent reusability, maintaining a Au recovery rate of ∼91 % after 10 cycles. Furthermore, fibrous adsorbents alleviated the pressure drop in columns filled with adsorbents, thereby enabling energy-efficient and environment-friendly processes.