Matos' last role was with the Portuguese giants' B team, where he acted as assistant coach.
But he will now link up with Klopp to hone the Reds' promises in a developmental role, having also accrued experience in China.
"Vitor Matos has officially joined the Liverpool FC staff as elite development coach," Liverpool announced on their official website.
Matos has taken in two spells at Porto, and also two years in China, and he will take up the role at Liverpool which was previously held by current assistant manager Pep Lijnders.
Klopp hopes that he will continue the work previously performed Lijnders in bringing through the next generation of talent.
“We’ve worked for a while on it. We had the idea that it makes real sense because we have so many outstanding, young boys," he said.
“The situation is a little bit like this: if you are in pre-season, they are with us and we need them for training, for the games and all that stuff. But then the season starts and all the big guns come back and we don’t want to give them the feeling they are now a bit further away again.
“So we thought it made sense that they really get their specific coach again what Pep did years ago when I came in. I loved the fact I got a sensational assistant manager, but we lost the development coach a little bit.
“We had to fill that void and we’ve done that with a really great guy, an outstanding coach. Young and experienced, you don’t get that a lot. A kind of guy who is used to having six or seven sessions a day.
“He is smart, his English is very good – which is obviously important – and he has worked at different clubs, but is educated at Porto, which is good for us because Pep is from there as well.
“He had made his own experience already and now we can all get the benefit of that. It will be great for the boys 100 per cent.
“We have to introduce him to the boys, but he will do that today.”