Archer has never taken the wicket of 12-time Ashes centurion Smith in a test match, but left him bruised and concussed after striking him in the neck with a 92mph bouncer on his fiery debut at Lord's in 2019.
Barbados-born Archer tore into the visitors in that series, claiming wickets including a career-best six for 45 in Australia's first innings at Headingley and again taking six wickets at The Oval as the series was drawn 2-2.
Injuries prevented Archer from appearing in the subsequent Ashes series, but the 30-year-old is now fit and firing and will be part of England's high-octane pace attack that many think could power them to a first series win in Australia since 2010-11.
"I think within the context of a test match and an Ashes match, there will clearly be that heightened sense of anticipation to see Archer up against Smith," ex-England bowler Finn, who will be part of the TNT Sports coverage team, said.
"I think Smith will be wary of (what happened in 2019) because Jofra is a very good bowler. But he was tweeting back to people the other day, reminding them that Jofra has never got him out in a test match.
"It's going to be a fascinating battle, and it could be a pivotal moment within the series. Both players will believe that they can win that situation, which will be riveting to watch."
Finn, who was part of the Ashes-winning 2010-11 team, says going after Smith with short-pitched bowling on Australia's hard tracks could be one ploy to try and stop the 36-year-old once again being a thorn in England's side.
"I think New Zealand had some success against him (Smith) doing that not all that long ago, maybe try and catch him unawares in that regard," Finn said.
He added that England's players would be foolish to think that 36-year-old Smith, who could possibly be playing his final home Ashes series, is on the wane.
"Judging by what I've seen in the Sheffield Shield over the last couple of weeks, I'd say he's still at the peak of his powers," said Finn.
"Statistically, if you look back at his last couple of years, they probably wouldn't be at the level that you would expect of Steve Smith.
"But one thing I do know about him is that he loves scoring runs against England, and he loves the pressure and the environment of an Ashes series.
"He's moved back to his favourable position of number four. He doesn't seem as obsessed with cricket as maybe he used to be, which I think at his age is something that's healthy to keep that fight and desire when you're out there in the middle.
"I would be very, very wary of Steve Smith if I were England."
The first test begins in Perth on November 21st.
