Taylor claimed victory in the inaugural BBC-televised tournament last year, defeating world number one Van Gerwen in both the group stage and the final as he took the £100,000 top prize.
Having won last weekend's World Matchplay, Taylor's rise to fourth on the PDC Order of Merit means that he will line up alongside Van Gerwen, Adrian Lewis and Van Barneveld in Group A for this year's Champions League of Darts.
With Taylor set to retire at the end of the year, the Champions League of Darts will be a final chance for fans in Wales to see the 16-time World Champion in competition as he bids to retain the title on September 16-17 at the Motorpoint Arena.
Group B will be headlined by two-time World Champion Gary Anderson and world number three Peter Wright, who has won the UK Open and reached the Premier League and World Matchplay final this year.
Two other Champions League debutants will also feature in Group B, with seven-time TV finalist Dave Chisnall and 2016 European Championship runner-up Mensur Suljovic set to challenge the two Scots during the group phase.
Following the three sessions of group matches, the top two players from each group will progress to Sunday evening's semi-finals and final.
"Last year's Unibet Champions League of Darts was a massive success on the BBC and this line-up sets the pulses racing ahead of September's tournament," said PDC Chairman Barry Hearn.
"Phil Taylor's amazing win in his final World Matchplay last week was a massive boost for him, and his win over Michael van Gerwen has spiced up their rivalry ahead of the Champions League.
"To have four World Champions in one group creates huge interest for the Champions League, but Group B is also mouth-watering with Gary Anderson, Peter Wright, Dave Chisnall and Mensur Suljovic all battling it out in Cardiff."
Tickets for the Unibet Champions League of Darts are available through motorpointarenacardiff.co.uk or by calling 029 2022 4488.
Unibet Champions League of Darts
1 Michael van Gerwen
2 Gary Anderson
3 Peter Wright
4 Phil Taylor
5 Adrian Lewis
6 Dave Chisnall
7 Mensur Suljovic
8 Raymond van Barneveld
Michael van Gerwen
Raymond van Barneveld
The schedule of play will be announced in due course.
Third In Group £15,000
Fourth In Group £10,000