Dolomite is an important industrial raw material for the production of metal magnesium. However, the calcination of dolomite is a typical pollution-intensive industry and is one of the major contributors to CO2 emissions in China. The requirements of energy conservation and environmental protection are driving the development of new calcination technologies. Herein, we developed a rapid and environment-friendly strategy for the calcination of dolomite used in subsequent magnesium production through carbothermal reduction, in which the pellets containing dolomite and carbon additive are calcined with in-situ Joule-heating in a vacuum. The effect of input volumetric specific power, heating time, vacuum conditions, carbon additive, and the size of the pellets on the decomposition process has been systematically studied. The dolomite in the pellets can be completely decomposed within tens of seconds. And the kinetic analysis shows that the activation energy of the decomposition of dolomite with the Joule-heating method is 108.4 kJ mol−1, which is much lower than the previous reports. Note that, the novel strategy shows a reduction of calcination time by 70 times, a reduction of energy consumption by 6.22% and a reduction of direct carbon emissions by 56.77% compared to the traditional methods. Combining the results of finite element simulations and density functional theory calculations, we revealed the mechanism of Joule-heating to enhance the decomposition of dolomite. The results show that the Joule-heating method can offer a distinct heating mechanism and deteriorate the structure stability of CaMg(CO3)2.