The invention discloses an apparatus capable of automatically monitoring exhaust emissions of vehicles on a real-time basis and an assessment method. The apparatus comprises a controller, an FPGA, a transmitting system, a receiving system, a PTZ driver, a camera, a radar speed measuring system, an RFID reader, a barometric pressure and temperature sensor, a 4G wireless transmission module and a data compensation memory table, wherein the transmitting system comprises a radio frequency driver, an acousto-optic tunable filter, an infrared light source, and a collimation system, and the receiving system comprises a first photoelectric detector, a signal processor, and a second photoelectric detector. The method improves the accuracy of exhaust gas measurement by digitally compensating for the influence of barometric pressure, ambient temperature, traffic speed, and inconsistency of the parameters of the first photoelectric detector and the second photoelectric detector on the exhaust gas measurement precision. The RFID technology is used to quickly identify traffic vehicles with exhaust emission exceeding standard and report to the traffic control department on a real-time basis, thereby improving the law enforcement efficiency of relevant departments.