The on-court announcer will introduce reigning Ladies' Singles champion Marion Bartoli and a child from the Elena Baltacha Academy of Tennis to Centre Court for the coin toss ahead of the opening match between last year's runner-up, Sabine Lisicki, and Julia Glushko.
Applause will be encouraged as a celebration of Baltacha's life, according to a Wimbledon official.
Usually a child is only involved in the coin toss on finals day when the chairman invites someone to nominate a charity which then puts forward a child to take part.
Traditionally at Wimbledon the Ladies' Singles champion opens play on the second day of the Championships.
As Bartoli will not be defending her title following her retirement, spectators will still have the opportunity to show their appreciation of her achievement, as well as remembering Baltacha.
Bartoli will be accompanied by nine-year-old Elle Robus-Miller - a young player from the Elena Baltacha Academy of Tennis, set up by the athlete to give children from all backgrounds the opportunity to learn to play tennis.
Baltacha died on May 4 from liver cancer at the age of 30, less than six months after marrying her former coach, Nino Severino, and weeks after retiring from tennis.
Baltacha retired from professional tennis after a career which had seen her ranked as the British number one for 132 weeks, from December 2009 to June 2012.
Her highest singles ranking was 49, which she reached in September 2010.
She dealt with a liver condition - primary sclerosing cholangitis, diagnosed at the age of 19 - throughout her career with medication and regular blood tests.
Despite the disruption it caused, she went on to win 11 singles titles and reached the third round of Wimbledon in 2002 and the same stage of the Australian Open in 2005 and 2010.
Baltacha represented Great Britain for 11 years in the Fed Cup but, after struggling with injury and illness during her career, ankle problems forced her to retire.
She then turned her attention to coaching junior tennis players at her Ipswich-based academy prior to her illness.
Andy Murray was asked yesterday if he had given any thought to donating some of his prize money to the Rally for Bally appeal, which aims to raise funds for The Royal Marsden Cancer Charity and Baltacha's Academy.
He told reporters: "I've done various things for Elena over the last few months. You don't have to make everything that you do public, as well."
Meanwhile, British player Tara Moore, 21, will be sponsored for fist-pumping during her matches at Wimbledon in what has been deemed a world first.
Mobile network Three will will donate £3 to Rally for Bally every time the British number five fist-pumps on the court.
The fist-pump is a commonly used gesture in tennis - with players including Murray and Maria Sharapova known to do it as they celebrate a point, game, set or match won.
Players are also able to wear white Rally for Bally wristbands, produced by British number two Laura Robson, who is not competing in this year's tournament due to injury.