The illustrious trio will be joined in the €2 million (US$2.96 million) showpiece by fast-rising American-Korean star Anthony Kim and newly crowned Asian Tour Order of Merit king Liang Wenchong.
The Ballantine's Championship, which will be held at Pinx Golf Club on the picturesque island of Jeju from March 13-16, is the first European Tour event to be held in Korea and is co-sanctioned by the Asian Tour and the Korea PGA.
Korean star Choi - who won the Sony Open in Hawaii on Sunday for his seventh PGA Tour victory - is relishing what promises to be a special homecoming.
"As someone who cares passionately about Korean golf I'm delighted that the European Tour is coming to my country for the first time," said Choi, the highest ranked Asian in the world at No.7.
"The Ballantine's Championship will be a huge boost to golf in Korea and I'm very happy to be playing in the inaugural tournament.
"It will be an emotional experience for me to be teeing off in front of the Korean fans and they can rest assured I'll be doing my very best to produce a home win," added Choi, 36.
World No.9 Harrington will also be one of the favourites to win the inaugural tournament. "It's great news that the European Tour is hosting its first event in Korea and I'm delighted to be taking part in this historic tournament," said the Irish ace.
"As players, we always look forward to new challenges and the Ballantine's Championship will be a tremendous opportunity to play in a different environment and meet new fans. It promises to be a fantastic event."
Harrington, 36, joined golf's elite with his victory in the 136th Open Championship at Carnoustie in July 2007, in the process becoming the first Irishman in 60 years to lift the Claret Jug.
Flying Scotsman Montgomerie, meanwhile, will head to Korea looking to add to his impressive record in Asia. "I've always enjoyed playing in Asia and have been fortunate enough to win in Hong Kong, Macau and mainland China in the past, so I'm very happy to be returning to the region for the Ballantine's Championship," he said.
"It's clear already that Ballantine's and the organisers are compiling an extremely strong field and all indications are that it will be a great addition to the European Tour schedule."
Montgomerie, 44, the most prolific British winner in European Tour history, finished 2007 on a high by teaming up with Marc Warren to win the World Cup for Scotland in China last November.
Fans at the Ballantine's Championship can be expected to show their backing for Kim, whose parents emigrated to the United States from Korea in 1971.
The talented 22-year-old from Los Angeles is enjoying a meteoric rise on the PGA Tour with five top-10 finishes to his name already and prize money of more than US$1.5 million in his first year.
"Playing in the inaugural European Tour event in the country of my parents' birth will be a great moment for me," he said. "I'll be banking on plenty of support from the fans and hopefully I can give them something to cheer about."
The Asian Tour's challenge at the Ballantine's Championship will be spearheaded by Liang, who will be looking to build on his successes of 2007.
China's No.1 achieved his maiden European Tour victory last March at the Singapore Masters and rounded off a brilliant year by becoming the first player from his country to win the Asian Tour's Order of Merit title.
"It's been a fantastic year for me and winning the Asian Tour UBS Order of Merit has allowed me to finish 2007 on a high," said Liang, 29.
"And, now, to be involved in the very first Ballantine's Championship in Korea, together with some of the best players in the world, means 2008 could be even better."
Simon Burley, marketing manager for Ballantine's, commented: "This is already an outstanding international field for the inaugural Ballantine's Championship. Ballantine's Scotch and golf share a tradition of excellence which we hope will be continued by a championship with stars of this calibre."
The Ballantine's Championship will be an "international" event open to all professionals, meaning entries will be determined by the Official World Golf Rankings rather than a player's position on any particular tour's Order of Merit.
Given this criterion, organisers are confident of creating a world-class field and more star players will be announced in the coming weeks.
The tournament, promoted by Parallel Media Group, is backed by the Korea PGA, European Tour and Asian Tour, which agreed earlier this month to co-sanction the event.
Ballantine's, the undisputed super premium whisky worldwide and in Korea, is the title sponsor and has committed to the event for a minimum of three years.