The invention discloses a wireless clock synchronization scheme of a positioning system based on TDOA technology. The positioning system includes a tag, a receiver, a time reference station and a positioning engine. The position of the receiver and the position of the time reference station are known. The time reference station periodically sends the clock reference data packet, and records the transmission time of the data packet and transmits it to the positioning engine. The receiver receives the time reference packet and records the reception time and transmits it to the positioning engine. The positioning engine obtains the time deviation between the receiver and the time reference station according to the transmission time of the clock reference packet, the reception time and the distance between the time reference station and the receiver. A group of time deviations are obtained from the transmission of multiple clock reference packets. The time deviations, frequency deviationsand drift differences between the receiver and the time reference station are estimated optimally by introducing the Kalman filter algorithm as an observation value. Finally, the time reference of thereceiver is unified to the time reference of the time reference station by using the information, and the clock synchronization of the receiver is realized.