Jo Whiley is to co-present a new, extended drivetime show with Simon Mayo, as Radio 2 overhauls its schedule.
Whiley will be the first female DJ on the station's weekday daytime schedule for 20 years.
Debbie Thrower was the last, presenting Radio 2's afternoon show between 1995 and 1998.
At a time when pay equality is under scrutiny at the BBC, Radio 2 confirmed Mayo and Whiley will earn the same.
In other changes to the station's line-up, Sara Cox will present a new show from 22:00 to midnight every Monday to Thursday.
Gary Davies replaces Cox on the popular Sound of the 80s programme while 6 Music's Cerys Matthews takes over the Blues Show from Paul Jones, who leaves the station after more than 30 years.
The Arts Show will be ending, as will The Organist Entertains – which has been on the network for almost 50 years.
Presenter Nigel Ogden thanked listeners for supporting the show over the last five decades.
"I've loved hearing from them and send them my very best wishes for the future. I'd also like to thank Radio 2 for giving me the opportunity to play the music I love each week. It has been a huge privilege."
Listen to the Band is also being taken off the air. Radio 2 says brass band music will continue to be played elsewhere.
The changes, which come into effect from 14 May, also see Robot Wars presenter Angela Scanlon added to the Sunday morning schedule, and OJ Borg presenting a live overnight show on weekdays.
'What a thrill'
Whiley, who joined Radio 2 in 2011, currently hosts a weeknight show specialising in new music.
She started her career as a researcher on Channel 4's The Word and hosted Radio 1's Evening Session with Steve Lamacq at the height of Britpop.
The new drivetime show is the first time she has shared the microphone with Mayo.
"Although we've known each other for over 20 years, we've never presented a show together," said Mayo in a statement. "And given that Jo is quite brilliant, it's high time we put that right."
"What a thrill to be working with Simon on this exciting new show," added Whiley.
"It's going to be great fun and listeners can look forward to some incredible music and chat, as well as being introduced to some fantastic new talent along the way. Cannot wait! "
Their pairing results in an extra hour of radio, with the drivetime slot extended from 17:00 to 20:00 every weekday, except Friday – when Tony Blackburn's Golden Hour remains from 19:00 to 20:00.
As a result, the weekly Blues, Jazz, Folk and Country shows will move one hour later – starting at 20:00 from Monday to Thursday.
According to figures published by the BBC last July, Mayo currently receives a salary in the range £350,000 – £399,999, while Whiley is paid £150,000 – £199,999.
Although they will receive equal pay for their upcoming show, there will still be a disparity in their total salaries, as Mayo presents a weekly show for 5 Live, and Whiley hosts events including Glastonbury for BBC television.