It should..
However, if I recall in version 6.1, number 0 referenced COM1 and 1 referenced COM2. It was a bit confusing, but was solved in LV7.
When you configure the port, do you wire the VISA reference or a number (0, 1, etc) as the port reference? If it is a number, then make sure 0 = COM1.
Other than that, LV and Win-XP should have identical COM port designation.
JLV