The magnetic hollow triple-shelled FeCo2O4 (TS-FeCo2O4) microsphere with 3D architecture was anchored directly on cotton cellulose fibers (CCFs) substrates through the solvothermal method with further dipping-calcination treatment. The formation mechanism of multi-shelled structure, which used beta-cyclodextrin as the template was discussed in detail. Comparison with pure single-shelled FeCo2O4 (SS-FeCo2O4), TS-FeCo2O4 and SS-FeCo2O4/CCFs, TS-FeCo2O4/CCFs displayed optimal dual-functional catalytic activities towards photodegradation of tetracycline (TC), malachite green (MG) and catalytic reduction of 4-nitrophenol (4-NP). The unique multi-shells and hollow interior structure of TS-FeCo2O4, the presence of metal oxide with 'd(7)' (Co element) and 'd(6)' (Fe element) electronic configurations, and the introduction of CCFs were beneficial to dual-functional catalytic properties. The possible dual-functional catalytic mechanism by TS-FeCo2O4/CCFs was deduced based on the Mott-Schottky, active species analysis and UV-Vis experiments. Because of the noticeable magnetic properties, TS-FeCo2O4/CCFs could be easily separated and reused. This work provided novel insights into the design and construction of high active 3D architecture dual-functional catalysts to remediation of organic pollutants.