The Spaniard will face European Ryder Cup captain Sam Torrance in the first round at the historic Wentworth Club in Surrey, England, with the winner to face Vijay Singh. Torrance replaced Canadian Mike Weir, who opted not to travel to the event.
In other first-round matches, Thomas Bjorn will meet Adam Scott with the winner getting defending champion Lee Westwood.
U.S. Open champion Retief Goosen will go against Ian Woosnam with Colin Montgomerie waiting for the winner.
Padraig Harrington will take on Nick Faldo as Darren Clarke faces the winner of that match.
Ballesteros was added as the 12th man after John Daly turned down an invitation to compete. The American, who shared second over the weekend at the German Masters, thought it would be better to come back to America to play at the Invensys Classic at Las Vegas in an attempt to crack the top-40 on the PGA Tour money list and qualify for next year's Masters.
Ballesteros won the event in 1981, '82. '84, '85 and '91, but has not competed in the championship since he was bounced by eventual champion Ernie Els in 1994.
Westwood titled last year, edging out Montgomerie on the 38th hole. His win marked a record-tying sixth of his season, but he has yet to collect a victory anywhere since.
Montgomerie, on the other hand, had owned Wentworth in recent times, winning on his last three occasions dating back to the '99 Volvo PGA Championship.
Thus far in 2001, the former seven-time Volvo Order of Merit champion has taken two titles, at the Murphy's Irish Open and the Volvo Scandinavian Masters.
The World Match Play Championship was first contested in 1964, with Arnold Palmer emerging victorious. The Wentworth Club has played host to the event every year.