Gunter made his international debut against New Zealand in 2007 and became the first male Wales player to reach 100 caps in 2021.
The former Cardiff City, Tottenham Hotspur, Nottingham Forest, Reading, Charlton Athletic and AFC Wimbledon right-back was part of Wales squads at three major tournaments, including the 2022 World Cup in Qatar.
He retired from international duty in March 2023 before ending his playing career two months later following his spell with Wimbledon.
FAW chief football officer David Adams said: “We’re delighted that Chris has accepted the opportunity to work with the next generation of Cymru players and lead our under-19s team.
“He’s someone who we identified through our combined Uefa A and B coaching programme four years ago, which was set up with the view of identifying a future international coach.
“Chris obviously brings a wealth of experience to the role having made more than 100 senior international appearances and featured at three major tournaments.
“We’re committed to keeping the players who were a key part of our success at Euro 2016 in our pathway and it’s clear to see Chris’ commitment to developing future international players.”
