In a threesome with the current and former world No.1s, Park Inbee and Tseng Yani, she is aiming to maintain a remarkable season's record of top-15 finishes in all the five majors.
At the LPGA Championship, she came close to adding another major to her 2009 Ricoh Women's British Open when she lost to Park in a play-off in New York State. She has also won this season, having collected her 11th career title with victory in the Aberdeen Asset Management Ladies' Open at Archerfield two weeks ago.
The Evian event has been accorded major status for the first time and the course, overlooking Lake Geneva, has undergone enormous changes since Park won the title under its guise as the Evian Masters last July.
"They have always made little tweaks here and there over the years," said 44-year-old Matthew, who has risen to a career-high No.7 in the world this week. "This time there have been major changes. It's very wet and playing very long after recent rain and it will be interesting to see how the scoring goes."
As the joint second richest tournament in the women's game - it and the US Women's Open both offer a first prize of £315,000 - it is disappointing that Matthew is the only Scot in the 120-strong field. Even Carly Booth, a two-time winner on the Ladies' European Tour last season couldn't earn a spot, although all 24 Solheim Cup players are in the line-up and the Europeans will be hoping that the momentum of their victory can be maintained.
Park has been on a roll all year, having won the first three majors before succumbing to the pressure at the Ricoh Women's British Open at St Andrews, a championship won in some style by Stacy Lewis, runner-up at Evian for the past two years.
A win this week would still make 25-year-old Park the first golfer to win four majors in one season, but she admits that the stress of trying to set a record is nothing compared to what she endured at the home of golf. "I think the pressure I felt at St Andrews will help me this week," she said. "I feel much more comfortable. Getting four out of five majors this year would be amazing."
Winner of the US Women's Open as a teenager in 2008, it was four years before she enjoyed that victory feeling again at Evian just 14 months ago. She has since won another seven times. "Winning Evian last July gave me a lot of confidence," she said. "Between the first two wins there were times when I thought I might never do it again. Sometimes I wanted to give up, but I stayed patient, kept my belief and waited for my time to come. Evian gave me hope, made me confident that I could go on and do what I've done this year."
Park picked out Matthew as one of her big rivals this week. "This is a course that will suit her game and I really enjoy playing with her," she said. "She's got a great chance."