Murray will lead the British team when they contest the Euro/Africa Zone Group I competition from 1-4 February 2012 in Eilat, Israel.
She will also work closely with the LTA player team in mentoring and supporting some of Britain's most promising female performance coaches.
Speaking about her new role, Murray said: "It is a huge honour for me to represent my country in this way, and the role presents a very exciting challenge, given the mix of talent, experience and determination we have in our top female players right now.
"I'm also really looking forward to working with the LTA to develop a bigger and stronger female coaching workforce.
"I want to encourage more women to get involved in coaching at the highest level, and to personally support their development."
LTA head of men's and women's tennis, Leon Smith, said: "To have someone of Judy's standing in the sport in such a key role for us is going to be a huge asset as we look to support our best players and coaches, and begin to climb up the ladder in world tennis.
"I know the players and the rest of the team are really excited about this."
Murray is one of Britain's most experienced and respected coaches after working as Scottish national coach for nine years and spending more than two decades working with both junior and senior players at all levels of the sport, including British number one Elena Baltacha, and British Davis Cup players Colin Fleming and Jamie Baker.