Hi mvut, 5V are to the VIN pin -
pin 23 (http://www.droids.it/images/990001_layout.jpg) . As far as I know, the VREF should be connected to the VCC with a max voltage of 3.3V, is it correct?
The XBee does not support 5V on ANY pin. The ONLY XBee that supports a 5V connection to any of its pins is the Cellular module. ALL others are only 3V devices and connecting 5V to them WILL damage them.
Remember that it is the radio that determines what voltage can be connected to it. NOT the adapter board. Not unless that board has a voltage divider or level shifter on it.