The 24-year-old Pole will be looking to go one better than his compatriot, 2012 finalist Jerzy Janowicz, in Paris.
He faces a mighty big hurdle to even get to the final as he plays world number one Novak Djokovic in Saturday's semi-final.
The Serbian world number one looked in ominous form as he eased past Taylor Fritz 6-4, 6-3 in just 73 minutes.
Fritz looked suitably disappointed as he went to the net to shake hands.
The American had thought with his recent run of good form and Djokovic returning to the circuit after a seven-week break he could record his first win in his fifth meeting with him.
Hurkacz may have more in the locker than the one-dimensional game of the American as he has shown in a break-out season for him.
"It is crazy," said Hurkacz referring to his Masters qualification. "The match was so hard today, knowing that I had to win the match.
"That obviously upped the pressure a little on me too."
Hurkacz had looked well in control as he eased through the first set 6-2.
However, 55th ranked Duckworth levelled the match with a commanding performance in the tie-break -- wagging his fingers at the crowd after taking it 7/4.
'Very big for me'
Seventh-seeded Hurkacz put real pressure on Duckworth in his first service game of the second set before the Australian took it after eight minutes of to-ing and fro-ing.
Duckworth took Hurkacz to deuce at 5-5 before the Pole held his serve but it was the Australian who came under pressure in the next game, saving two match points.
Hurkacz, though, took the match at the third opportunity, the Wimbledon semi-finalist raising his arms and then punching the air in delight.
"You dream about it as a kid, and you're, like, when you're growing up you don't know if it's gonna be possible, if you're gonna be good enough," said Hurkacz of reahcing the ATP Finals.
"Now achieving this thing, it's very big for me."
Djokovic took his seven-week break when his dreams of a Grand Slam sweep were dashed by Daniil Medvedev in September's US Open final.
Medvedev, the Paris title holder, has hopes too of wresting the world number one spot from Djokovic by the end of the season.
The 25-year-old Russian plays surprise package Frenchman Hugo Gaston in a quarter-final later on Friday.
Should Gaston -- who won seven games in a row from 5-0 down to win the second set and the match against Spanish teenager Carlos Alcaraz on Thursday -- beat Medvedev, Djokovic would be assured of finishing the year as number one for a record seventh time.
The other quarter-final pits last year's finalist, Olympic champion Alexander Zverev, against Norway's six-seeded Casper Ruud.
The match brings together the only two players to have won five titles apiece this year, that feat propelling Ruud to a first ever ATP Finals appearance for a Norwegian player.