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Chain-spherical V 2 O 5 /C composites were prepared by using dandelion fibers as bio-templates through a simple vacuum-assisted immersion method, and their microstructure and electromagnetic wave (EMW) absorption properties were investigated. Results indicated that the EMW absorption performance of dandelion fibers is effectively improved by introducing V 2 O 5 and constructing chain-spherical structure. Notably, the minimum reflection loss (RL min) of V 2 O 5 /C composites with a thickness of 2.35 mm is reached −34.05 dB at 17.52 GHz, and the maximum effective absorption bandwidth (EAB) of the composites is up to 7.52 GHz at 2.85 mm. The improvement in EMW absorption performance is mainly ascribed to the synergistic effects of the increased multiple reflections and scattering, enhanced polarization loss and conduction loss, and impedance matching characteristics. The chain-spherical V 2 O 5 /C composites exhibit great potential as promising candidates for high-performance EMW absorbers. • The V 2 O 5 /C composites with a chain-spherical structure are facilely prepared. • The synergy effect of multiple loss mechanisms enhances microwave absorption. • The RL min of −34.05 dB and the widest EAB of 7.52 GHz are achieved. [ABSTRACT FROM AUTHOR]