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The former Ramsay Street sweethearts will be the centrepiece of Friday night's Hit Factory Live concert in the English capital as they present their much-loved duet.
Concert organisers this week revealed Minogue's involvement, having previously advertised only a "very special guest".
"The Hit Factory audience are in for a very special treat as Kylie Minogue is confirmed to bring the show to an unforgettable end by performing with Jason (Donovan) on Especially For You," a statement said.
"They last performed it together in 1989."
The concert celebrates the work of songwriting and production team Stock Aitken Waterman, which penned several hits including Especially For You.
Released in November 1988 - after Minogue had left the cast of Neighbours where she played the part of Charlene alongside Donovan's character Scott - the single achieved prolonged chart success in Australia, New Zealand and the UK, along with other European countries.
A spokeswoman for Hit Factory confirmed the pair has never performed the song live, although Minogue has included the tune in some of her tours and sang the duet with Kermit the Frog for a TV special in 2001.
Minogue and Donovan's reunion was initially scheduled for July but the outdoor Hit Factory concert had to be postponed due to rain.
Before the delay, Minogue had spoken of the hype she expected as she took to the stage with her former Neighbours husband.
"I don't think we'll even need to sing it. I'm sure the audience all went through the Neighbours wedding. It's going to bring the house down," she told Glamour magazine.
Especially For You will end a concert that includes performances by Bananarama, Rick Astley, Steps, Dead or Alive, Sinitta and others.