The invention provides a measurement system for rapidly measuring thermoelectrical potential. The system mainly comprises a sample table provided with a first supporting copper block and a second supporting copper block, a temperature measurement and control module provided with a temperature controller, a first temperature sensor, a second temperature sensor, a first heating block and a second heating block, a thermoelectrical potential measurement module provided with a nanovoltmeter, and a data processing module provided with an A/D (Analogue to Digital) conversion device, a data transmission bus and a data processing unit. The invention further provides a measurement method for rapidly measuring thermoelectrical potential by using the measurement system. Compared with the prior art, according to the measurement system and the measurement method for rapidly measuring the thermoelectrical potential provided by the invention, the thermoelectrical potential of the test sample can be quickly, conveniently and rapidly measured without operations such as gold-plating treatment on the surface of the sample to be measured and welding, and roughness and evenness on the surface of the sample to be measured are not strictly required, and the error is smaller when the sample to be measured with smaller thermoelectrical potential is measured.