The move means Shabana Mahmood, formerly universities and science minister, has lost her higher education brief after two years in the post.
Mr Byrne, seen as a Blairite, was demoted from shadow work and pensions secretary in the reshuffle.
When Labour lost the election in 2010, Mr Byrne left a notorious note to his successor as chief secretary to the Treasury stating that there was “no money” left.
He holds a degree in politics and history from the University of Manchester and an MBA from Harvard University.
Ms Mahmood, a new MP elected in 2010, was appointed as shadow minister for higher education in October 2011, shortly after Ed Miliband announced that Labour would lower fees to £6,000 if it were in power. She gained the additional science brief earlier this year.
Meanwhile, academic Tristram Hunt has been appointed as Labour’s shadow secretary of state for education.
Mr Hunt, who teaches history at Queen Mary, University of London and is MP for Stoke-on-Trent Central, was promoted from a more junior education role.
Seen as a Blairite, he told Times Higher Education in 2012 that he wanted to see further education colleges and sixth form colleges to rekindle the “polytechnic brand”.
As yet there has been no change in the position of David Willetts, the universities and science minister, as David Cameron undertakes his own reshuffle in the Conservative ranks.