Mylrea will become the head of press and media relations at the corporation on 6 April, reporting to director of comms Ed Williams.
He replaces long-term media chief Donald Steel who, as announced in November, moves on to the newly created role of chief communications adviser at the BBC.
This news follows the election of Mylrea as 2011’s CIPR president last December.
Mylrea said: 'The BBC has a unique relationship with both the public and the media and faces the challenge of constant and increased scrutiny.'
He is expected to be dealing with the frequent high-profile media stories that hit the corporation - a recent example being the £639 taxi expense claim by BBC technology chief Eric Huggers.
The job specification states that the job ‘sits at the heart of reputation management for the BBC’. It is ‘central to managing the audience’s media influenced perception of the role and value of the corporation, and is intimately involved in BBC issues of national and international importance’.
Mylrea will lead the BBC press office and strategic comms function and is part of a ten-strong communications steering group. He will also be the BBC's official spokesman.
Before joining DfID in 2007, he worked as director of group media relations at Transport for London and head of media at Oxfam GB. He has also worked as a journalist at Reuters.
The BBC underwent a comprehensive review of its comms function last October, which has seen all comms staff come together to form one team under the leadership of Williams.