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Silicon waste (SW), a byproduct from the photovoltaic industry, can be a prospective and environmentally friendly source for silicon in the field of thermoelectric (TE) materials. While thermoelectricity is not as sensitive toward impurities as other semiconductor applications, the impurities within the SW still impede the enhancement of the thermoelectric figure of merit, zT . Besides, the high thermal conductivity of silicon limits its applications as a TE material. In this work, we employ traditionally metallurgical methods in industry reducing the impurities in SW to an extremely low level in an environmentally friendly and economical way, and then the thermal conductivity of purified silicon is greatly reduced due to the implementation of multiscale phonon scattering without degrading the power factor seriously. Benefiting from these strategies, from 323 to 1123 K, for the sample made from purified silicon waste, the average zT , relevant for engineering application, is increased to 0.32, higher than that of the state-of-the-art n-type Ge-free bulk silicon materials made from commercially available silicon, but the total cost of our samples is negligible.