Sandé walked away with 'British Female' and 'British Album' for Our Version of Events at the ceremony, which took place at London's O2 Arena.
> Brit Awards 2013: Winners in full
"I think I'm a very unlikely popstar. This is an album I wrote because I didn't have the confidence to say these things myself as a person," Sande said while collecting her 'British Album' award.
Mumford & Sons beat One Direction to the 'British Group' prize, while Ben Howard walked away with the 'British Breakthrough' award, which was voted for by BBC Radio 1 listeners.
Howard also triumphed in 'British Male', saying: "I was quite stoked to come to the awards to be honest, so to come away with two of these things is quite amazing."
Adele's James Bond theme 'Skyfall' was named 'British Single' and the star appeared in a pre-filmed clip to thank fans and mock her speech being cut off at last year's ceremony.
Lana Del Rey won 'International Female', Frank Ocean bagged the 'International Male' award and The Black Keys won 'International Group'.
Coldplay walked away with the 'British Live Act' award for their sold-out Mylo Xyloto stadium tour.
One Direction left with the 'Global Success' award, having topped the charts across the globe during 2012.
"This really is absolutely mid-blowing," said Louis Tomlinson, before thanking their "incredible" fans.
Gallery - Brit Awards 2013 winners in pictures