The UART example code from C:\ti\msp430\MSP430ware_1_00_00_00\examples\devices\5xx_6xx\MSP430F563x, MSP430F663x Code Examples\C says that the USCI_A0_UART TX and RX functions appear on P.0 and P.1 (see sample header below)
// Note that UCA0RXD and UCA0TXD need to be assigned pins via the PMAP
// controller.
//
// MSP430F66x
// -----------------
// /|\| |
// | | |
// --|RST |
// | |
// | P2.0/UCA0TXD|------------>
// | | 9600 - 8N1
// | P2.1/UCA0RXD|<------------
//
// Priya Thanigai
// Texas Instruments Inc.
// Nov 2009
// Built with IAR Embedded Workbench Version: 4.20 & Code Composer Studio V4.0
However, the F6638 datasheet says that USCI_A0_UART appears on P2.4 and P2.5.