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In view of shortcomings exist in traditional toll mode of expressway and some defects of electronic toll collection system, such as short distance, high cost, and poor security. A kind of radio frequency chip, nRF9E5, was adopted to design electronic toll collection system of expressway. Structural and process designs were made, in addition, a new RFID authentication and authorization protocol model was used to guarantee system security. The electronic toll collection system based on RFID has advantages of less cost, small size and high reliability. It is very suitable for practical application.