Ectomycorrhizal fungi can enhance the tolerance of plants to heavy metal stress by reducing the accumulation of heavy metals in the aerial parts of the plants. Extracellular chelation is a major mechanism of heavy metal tolerance in ectomycorrhizal fungi in which extracellular slime plays a fundamental role. The objectives of this study were to investigate the potential metal-binding ability and the protein composition of extracellular slime. The extracellular slime of Laccaria bicolor (L. bicolor) cultivated under Cd2+ and Cu2+ stress was separated using various ultrasonic pre-treatments. The protein content, composition, and metal content of the extracellular slime were measured. The results showed that the protein content in the extracellular slime significantly increased under both Cd2+ and Cu2+ stress. The SDS-PAGE profile showed that Cd2+ and Cu2+ stress induced the expression of several new proteins. Heavy metal quantification revealed that the Cd content fixed in the extracellular slime accounted for 22-28% of the metal fixed by the fungal mycelia. Meanwhile, no Cu was detected in the fungal extracellular slime, implying that the extracellular slime may not be effective for the fixation of essential metallic elements such as Cu. Taken together, these results provided evidence that L. bicolor was able to ameliorate the intracellular Cd content by stimulating extracellular slime exudation and altering the composition of the proteins therein. Nevertheless, this blocking strategy may be effective only for the non-essential element Cd and was ineffective for the physiological element Cu.