Traditional photocatalysts for Cr(VI) often suffer from low catalytic activity, difficult separation and recovery, and weak stability. To address these limitations, we proposed a spherical sponge-inspired design to construct chitosan/silver cluster-loaded cellulose nanofibrils/Cu-ZIF-8 gel beads (CSCZ). This design featured a chitosan-based gel bead (the shell of the spherical sponge), silver cluster-loaded cellulose nanofibrils (the flagella of the spherical sponge), and Cu-ZIF-8 (the collar cell of the spherical sponge), which collectively endowed the CSCZ with remarkable properties. These included a high adsorption capacity (171.2 mg/g), a notable rate constant (0.2812 min−1), and enhanced stability (retaining 84.9 % of its initial removal rate after 10 cycles). In addition to the structural design, the “adsorption–reduction” synergy significantly enhanced Cr(VI) removal efficiency, as confirmed by both experimental characterizations and theoretical calculations. Furthermore, the CSCZ was utilized to treat industrial wastewater, and a custom-built flow-through reactor packed with CSCZ demonstrated the efficiency and practicability of CSCZ. This study demonstrates CSCZ’s potential to efficiently remove Cr(VI) and advances the development of photocatalytic adsorbents inspired by spherical sponge concepts.