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High electrical conductivity crystals were selectively precipitated from vanadate glasses by microwave heating. Both the V2O5 and the CuxV2O5 (x = 0.26-0.55) crystals were precipitated in a conventional electric furnace, but CuxV2O5, which has an electrical conductivity about 106 times higher than V2O5, was precipitated preferentially by microwave heating. The conductivity of the glass crystallized by microwave heating was three times higher than that of the glass crystallized by conventional heating. In addition, the Seebeck coefficient of the microwave crystallization glass was about two times higher than that of the conventional crystallization glass. The power factor was improved about 12 times by microwave crystallization.