The 'Next To Me' singer was confirmed to appear on the first live show on the programme's official Twitter feed.
"Our first confirmed guest performer for #TheVoiceUK live shows is... @emelisande! She's amazing. We're excited. Details soon," the announcement read.
The first live show of The Voice UK will air in May, following the battle rounds later in April.
Sandé scored a number one album with her debut Our Version of Events earlier this year.
The singer-songwriter recently worked with the original lineup of the Sugababes on their upcoming comeback album.
The Voice UK is set to avoid clashing with ITV1's Britain's Got Talent from April 21 onwards.
> Emeli Sandé: 'I'd love to finish my medical degree'
Watch the video for Emeli Sandé's 'Next To Me' below: