Lee played 76 Tests for Australia from 1999 to 2008, taking 310 wickets. He also took 380 wickets in 221 one-day internationals.
Lee first played for a Prime Minister's XI against India in 1999, taking four wickets. Three weeks later, he played his first Test against India at the Melbourne Cricket Ground.
Officials said on Wednesday that the remainder of the invitational side would be named later this month.
The Prime Minister's XI match follows England's five-Test Ashes series and be held in between the first and second of five one-day internationals against Australia. England will also play two Twenty20 matches against Australia in late January.
The Ashes: Brett Lee to captain Prime Minister's XI against England
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