Voltage measurement is an important part of power system operation, and non-intrusive voltage sensors have the advantages of low insulation difficulty, simple structure, easy loading and unloading, and high construction safety, which have become a new direction for voltage measurement. Based on the principle of electric field coupling, this paper constructs a non-intrusive floating ground three-capacitance voltage measurement model, which can complete the accurate measurement of voltage without connecting with the line to be measured and the earth in the measurement process. In non-intrusive voltage measurement, the change of the object to be measured or the measurement environment will cause the change of the coupling capacitance, which leads to the uncertainty of the transmission relationship of the sensor and the large error of measurement results. In order to solve this problem, a new method of sensor calibration is proposed in this paper. By sampling capacitance in parallel between two electrodes of the sensor, changing the capacitance value, and establishing an input output equation, the coupling capacitance value and the voltage value to be measured under different operating conditions are solved. In addition, the sampling capacitance is often several orders of magnitude larger than the sensor’s own capacitance, making the sensor’s voltage division ratio significantly higher and more conducive to the measurement of high voltages. The experimental results show that the measurement error is less than 2%, which verifies the feasibility of the method and the accuracy of the voltage measurement.