Abstract: The affect of the chemistry on the thermoelectric character of natural black tourmaline is tested, which is from Xinjiang, Inner Mongolia and Yunnan Province. The mechanism of thermoelectric character is designated. It shows that there is much difference in chemical composition of natural tourmaline from different regions, in which the content of ferric oxide will obviously affect the thermoelectric character. With the increase of the content of ferric oxide, the effect of thermoelectricity decreases. The thermoelectric character of tourmaline has better corresponding relation to normal physical character. We can indirectly understand the thermoelectric character of tourmaline through examining the density and refractance.