This study explored a possible destruction of hexachlorobenzene (HCB) as example of persistent organic pollutants (POPs) as well as the dechlorination mechanism by directly using minerals in the soil, such as antigorite, talc and olivine. Compared with a stable quartz phase of SiO2, all three Mg silicate minerals demonstrated certain degrading capacity for HCB with different efficiency order as: antigorite > talc > olivine > SiO2 at 2 h of milling time. Interestingly, olivine exhibited a better performance than antigorite at 4 h of milling time, giving destruction percentage of 92.7% over 89.0% even at high concentrated HCB up to 5% added. Raman and ESR characterizations of the ball milled sample with olivine indicated the formation of amorphous carbon and graphitic carbon, and the occurrence of free radicals was observed to play an important role in dechlorination and carbonization of HCB. The first identified effectiveness of directly using Mg silicate minerals, allowed no addition of active chemicals during the ball milling, therefore avoided the concern over extrinsic contaminations on the soil. Olivine was further utilized to deal with actual contaminated soil and showed unique advantages on application prospects.