Seven years after he was awarded a Cam Smith scholarship, the 23-year-old will play under Smith, who captains the all-Australian Ripper GC team that also features Marc Leishman and Lucas Herbert.
The 23-year-old rising star won the 2024 Australian PGA championship - beating Smith.
It continues a big few days for LIV following Brooks Koepka's decision to return to the PGA Tour and Smith announcing on Wednesday he was staying on the breakaway circuit.
Belgian Thomas Detry and South Korean Byeong Hun An have also joined LIV. Smylie will replace Matt Jones in the Ripper GC team.
"I believe this is the next step for me in order for me to become the golfer I want to be," Smylie told journalists on Thursday morning.
"You look at the roster here, there are so many major champions ... this is the next step for me, to try and learn as much as I can off them.
"Playing globally is a big goal of mine. Week-in, week-out, you're always learning so many different things and you're always adding tools to your toolbox."
The son of former tennis professional Liz Smylie said Koepka's decision to leave LIV did not impact his decision to join the circuit.
"Everyone has their own reasons ... it didn't have any repercussion on why I wanted to join," Smylie said.
He is also confident of retaining his relationship with mentor and Australian PGA player director Adam Scott, despite the LIV defection.
"Even though it is a different path to what he's gone down, I think he will have my best interest," Smylie said.
"I still believe he and I can keep a great relationship."
Smylie also remains upbeat about playing in golf's four majors as a LIV player.
"LIV is definitely the priority, but I would like to try and play as many DP World Tour events as I can," he said.
"At the end of the day, good golf always takes care of itself."
Smylie was a spectator at last February's LIV event in Adelaide and negotiations started around that time.
"I truly do believe that it's growing the game in a healthy way. Conversations did start maybe 11 months ago and as each month's progressed, I've obviously been playing quite well over in Europe," he said.
"It's going to be really cool, being on the other side of the ropes (in Adelaide) - you're going to feel feelings that you can't practise in training."
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