Mills, who has been on the radio for more than two decades, on Monday replaces former breakfast show presenter Zoe Ball, who helmed the show for more than half a decade until December.
In the coming week, Trevor Nelson is picking up Mills’s previous weekday 2pm to 4pm slot.
Mills told Channel 4 show Sunday Brunch: “I’m so excited.
“Obviously, I’ve been on the radio for a very long time, people have kind of listened to me at school and college and (university) and got married and sometimes divorced.
“But this feels like… a brand new start.
“I think when I was on Radio 1 I filled in on the Breakfast Show, more than anyone else in history, but it’s never been my show.
“So it’s big, the biggest show in Europe, I mean I am nervous, but then you have people go, but why? Yeah, I think it’s good nerves.”
The 51-year-old also said it would be a change to his afternoon show, as “a lot of people, waking up, this is the first time… (they) check social media”.
Mills added: “I want it to be as well as great music, stuff that you didn’t know that’s happening right now, what’s happened overnight.”
When asked if that meant politics, he laughed.
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Ball was the BBC’s highest-paid on-air female presenter in 2023/24, with a salary between £950,000 and £954,999, ranking her second on the list of top-earning talent behind Gary Lineker, according to the corporation’s annual report published in July.
Mills had a 2023/24 salary of £315,000 to £319,999, the report said, up from £300,000 to £304,999 during the previous period.
Ball, who took over from Chris Evans in January 2019, has had the biggest audience of listeners for any breakfast programme in the UK, according to the audience research body Rajar.
