An apparatus and a method for providing an interworking service with a peripheral device in a Mobile Station (MS) supporting one or more wireless connectivity protocols are provided. Information on an execution environment of an application program for the interworking service is checked when the application program for performing the interworking service with the peripheral device is executed. A wireless connectivity protocol is selected from among the one or more wireless connectivity protocols for performing the interworking service with the peripheral device using the information on the execution environment of the application program.