Smith, who won solo bronze at the Delhi Commonwealth Games in 2010, called time on her career in September 2011 after several years as part of the British team based in Aldershot.
She worked for LOCOG before and during the London 2012 Olympics last summer and replaces Adele Carlsen as the high performance manager of the British team.
Carlsen worked alongside national performance director Biz Price since 2007, encompassing the Beijing and London Olympics, but moved on after last summer's Games.
Smith cannot wait to start helping both her former team-mates and the new additions to the squad.
"I am extremely excited to be taking up this role with the team," she said.
"As an athlete for 18 years and then working with LOCOG in planning and running the Olympic Games, I feel this is the perfect next step in my career.
"I am looking forward to helping British synchro fight for their place and world ranking at the Rio Olympics.
"I am also excited about the World Championships this year, which will be my first major competition with the team.
"I have experience of World Championships as an athlete and it will be good to see it from the other side.
"There are a number of new athletes in the team and I am looking forward to seeing the final masterpiece of their first year's work."
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