The utilization of biomass materials with functional properties and rational porous structures holds significant potential for the recovery of precious metals from secondary resources, while facing challenges in achieving rapid reduction and high recovery rates of metallic Au(0). Herein, a novel concept of achieving high-purity Au(0) efficiently by tailoring tannin acid (TA) architecture and porous structure of TA-functionalized alginate beads (P-TOSA). Optimized by structural engineering, the hierarchically nanostructured P-TOSA beads demonstrate exceptional selectivity and recovery capacity (756.1 ± 2.7 mg/g at pH 5), while maintaining a recovery efficiency of over 99 % across a broad range of pH values (1.0–8.0) through the synergistic combination of chelation-based chemisorption and phenolic groups-based redox reaction. Notably, the TA-based nanostructure-boosted reduced Au(0) served as nucleation sites, facilitating elongation and migration of gold crystals across the vein network, thus forming a shell composed with 90.4 ± 0.4 % of element gold. UV radiation exposure could further generate a dynamic redox system and expedite Au (III) reduction to ultra-high purity Au(0) (93.3 ± 1.1 %) via abnormal grain growth mode. Therefore, this study presents a practical and straightforward approach utilizing biomass microbeads for recycling precious metals in metallic form without the use of toxic eluents or additional reductants.