An apparatus and method for selecting a Proximity Interface Coupling Card (PICC) of a portable terminal having a Near Field Communication (NFC) module including multiple PICCs are provided. The method includes activating the NFC module when the portable terminal is at a power-off state, determining whether a key signal for activating one PICC among the multiple of PICCs is inputted in the activated NFC module, and activating the PICC mapped with the inputted key signal when the key signal is inputted.