A white rot basidiomycete, Ceriporiopsis subvermispora, degraded vulcanized natural rubber (NR) sheets on a wood medium. The fungus decreased the total sulfur content of the rubber by 29% in 200 days, accompanied by the cleavage of sulfide bonds between polyisoprene chains. X-ray photoelectron spectroscopy (XPS) demonstrated that C. subvermispora reduced the frequency of S-C bonds by 69% with a concomitant formation of S-O bonds during the culture period. Dipolar decoupling/magic angle spinning (DD/MAS) solid state 13C NMR revealed that the fungus preferentially decomposed monosulfide bonds linked to a cis- and trans-1,4-isoprene backbone but the cleavage of polysulfide bonds was also observed. In contrast, no decrease in weight or devulcanization of rubber was observed in cultures of a white rot fungus, Dichomitus squalens. The oxidative cleavage of sulfide bonds by C. subvermispora demonstrates that ligninolytic basidiomycetes are potential microbes for the biological devulcanization of rubber products.