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Munchetty framed the transition as a natural progression after hosting the station's mid-morning slot since 2021.
"Presenting a flagship programme on 5 Live is an opportunity that was simply too good to pass up," she said.
She noted her goal to expand her relationship with morning radio listeners.
"Over the last five years, I've been privileged to build a relationship with 5 Live listeners on the mid-morning programme," she said.
Munchetty confirmed she will continue her regular hosting duties until the schedule changes take effect.
"Between now and January, I'll continue presenting the two programmes I love," she said.
Co-presenter Jon Kay shared the news with viewers on air.
"Our friend and colleague Naga Munchetty has announced that she will be leaving BBC Breakfast to co-present the BBC 5 Live Breakfast Show from January next year," Kay said.
Co-anchor Sally Nugent confirmed that the current radio presenters had been informed.
"Naga has just shared the news with the current presenters Rachel Burden and Rick Edwards," Nugent said.
Rachel Burden will move to the weekday mid-morning slot from Monday to Wednesday after 15 years on 5 Live Breakfast.
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Rick Edwards will transition to present Fighting Talk on Saturday mornings. The BBC has begun recruiting Munchetty's successor on the television sofa.
