Here is reported a self-priming electrostatic particulate matter (PM) sensor for real-time monitoring of diesel exhaust under different operating conditions. Initially, a multi-physics coupling model for the sensor was established. By varying the exhaust flow and temperature, the emissions of diesel vehicles were simulated to evaluate the sensor. The results showed that within the typical velocities (5 to 60 m/s) and temperature ranges (100 to 500 °C) of diesel exhaust, the sensor outlet pressure was consistently below the inlet pressure, with a maximum differential pressure of 259 Pa, indicating the capability for self-priming sampling of exhaust under different operating conditions. Additionally, the calibration platform was constructed using a miniature inverted soot generator which produced a series of samples to calibrate the relationship between current and mass concentration with a correlation coefficient of 0.99. From 0 to 100 mg/m3, the PM sensor exhibited a relative error between −6.00% and 6.00% with good stability and consistency for samples of different sizes and concentrations, with correlation coefficients exceeding 0.98. The results between the self-developed sensor and a commercial instrument revealed that the former provided high-precision real-time measurement of diesel exhaust.