The Outlander favourite, who is nominated for her role in Belfast, looked the picture of glamour in a black velvet number with a daring V-neckline and eighties inspired shoulder pads. The floor-sweeping gown boasted a triangular cut-out at the neck, long sleeves and a curve-skimming fit, with subtle diamanté embellishment on the train.
WATCH: Why there's so much hype around Jamie Dornan film Belfast
Caitriona ensured her dress took centre stage by keeping her hair simple, pinning her brunette locks back in an elegant updo.
She opted for a slick of plum-coloured lipstick and brightened up her look with a dusting of rosy blusher and matching pink eyeshadow. Caitriona opted for blush-toned accessories too, sporting a gorgeous opal ring and beautiful drop earrings.
Caitriona Balfe looked beautiful in an elegant velvet dress
The star is nominated as Best Supporting Actress for her role as Ma in Belfast, which landed six nods despite director Sir Kenneth Branagh being snubbed in the Director category.
The drama, which stars Jamie Dornan and Dame Judi Dench, depicts Kenneth's childhood in Northern Ireland at the time of the Troubles.
Caitriona is up for Best Supporting Actress in Belfast
Caitriona was joined by the likes of Salma Hayek, Emma Watson and Lady Gaga on the star-studded red carpet.
This year's BAFTAs, hosted by Rebel Wilson, were not attended by Prince William and his wife Duchess Kate due to a scheduling conflict.
The Outlander star wowed on the BAFTAs red carpet
The 75th EE British Academy Film Awards celebrated the very best of British and international film talent.
Speaking about her hosting gig back in January, Hollywood star Rebel said: "I am very honoured to be hosting the EE British Academy Film Awards in March, where Covid will no longer exist because it will clearly have been cancelled by then. It's going to be so much fun!"
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