The invention relates to a trace dissolved oxygen tester on-line calibrating device and a calibration method thereof. The method is based on the Faraday's law of electrolysis, and the device comprises a fiber filter, a flow control system, a Faraday electrolysis device, dissolved oxygen measurement equipment and a control device. The trace dissolved oxygen tester on-line calibrating device and the calibration method thereof are reliable in design theory, simple and convenient in method and great in operability. According to the trace dissolved oxygen tester on-line calibrating device and the calibration method thereof, field sample water is used, the process of preparing ultra-pure water is omitted, and the process of taking out an oxygen electrode is avoided through on-line calibration. Water electrolysis efficiency is measured on line, so that electrolysis efficiency variation caused by water sample variation and instability of an electrode can be tracked, and the calibration result can be more accurate and reliable. Calculation of electrolysis efficiency of the field sample water is applied to a high precision gauge pressure sensor, and accuracy of electrolysis efficiency calculation is guaranteed.