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Vanadium slag contains high contents of vanadium and chromium with complex and dense structures, hence microwave heating instead of conventional methods is expected to destroy the dense structure and further to improve the extraction rate of vanadium and chromium, and exploring its dielectric properties is the prerequisite work. Microwave absorption properties and thermal behavior of vanadium slag were investigated. Results indicated that vanadium slag endowed excellent microwave absorption properties, with minimum εr' value of 34.447 (