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In order to solve the problems of high failure, different network standard and inconvenience in tradition Electronic Toll Collection System(ETC). This paper discuss the application of RFID-SIM card in Electronic Toll Collection System in expressway. Furthermore, it analyzes hardware structures and connection among each module of the RFID-SIM cell phone's payment system, its application in ETC and some difficulties, and uses the electronic tag and conflict detection to deal with the uncontrollable distance of swiping card and conflict of swiping card in the application. Based the study it can sure the RFID-SIM card will have wide application prospects in ETC with its Convenience and intelligent.