The 44-year-old, who was born in Kingston, will take up duties in November after agreeing a one-year deal with the Jamaica Football Federation.
Barnes takes over from Brazilian Rene Simoes, who was sacked as technical director last week.
JFF president Horace Burrell said: "The board of directors of the JFF have approved the appointment of John Barnes, former England international, as the head coach of the national senior team, commencing November 1, 2008.
"The board have approved his appointment for a period of one year, which will be up for review, and possibly renewal."
The post is Barnes' first job in management since an ill-fated spell in charge of Celtic in 1999-2000.
Barnes made 40 appearances for Newcastle between 1997/98 J.Barnes scoring seven goals.
A class player, but far past his best when he joined Newcastle.
He had very little pace when he arrived from Liverpool and some said it was an "old pal's act" by Kenny Dalglish.
Joined Charlton Athletic after Newcastle.