Vamvakaris is no stranger to the sport, having been assistant manager of the Greek men's team as they finished ninth at London 2012.
At last year's Olympics Great Britain's women finished eighth as they failed to win any of their matches.
But following his appointment Vamvakaris is hoping to turn the team's fortunes around with all eyes on Brazil in three years time.
"It is a great privilege to become head coach of the GBR national water polo team," he said.
"I promise to deliver the best possible results and I look forward to using all of my knowledge and experience to drive the team forward.
"The role will need a lot of work and real trust to lead us to our goal which is a place at the Olympic Games in 2016. I am looking forward to getting started."
Graeme Thompson, national performance director for water polo, added: "After a rigorous recruitment process, I am delighted to announce the appointment of Konstantinos Vamvakaris.
"He brings a wealth of coaching knowledge including the experience of the London 2012 Olympics, where he was the Greek men’s assistant coach.
"From our first meeting he demonstrated a strong passion and desire to drive GB Women’s Water Polo to the Rio Olympics and be amongst the top nations in the sport."
© Sportsbeat 2013