The Bite Me singer, 37, wowed in a dramatic punk rock-inspired look, donning a custom-made black tulle gown from MOI MOI Paris with a leg-baring mullet hem and a puffball tiered skirt. The low-cut number boasted a fitted bodice with feather embellishment on the shoulders and a sash cinching her in at the waist, emblazoned with the name of her latest album, Love Sux. Avril accessorised with a pair of towering, studded platform heels and layered silver necklaces.
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She wore her long, orange-tipped hair in loose waves and opted for a flick of feline winged eyeliner and pale pink lipstick.
Looking more loved-up than ever, Avril walked the red carpet arm-in-arm with rocker Mod Sun, who showed off his extensive tattoo collection by going shirtless under his tuxedo jacket.
The pair posed for a kiss as they made their way into the MGM Grand Garden Arena for the ceremony, where the singer was on presenting duties.
Avril was in high spirits at the Grammys, reflecting on her comeback in a chat with E! News. She said: "This year is my 20th anniversary since my first album 'Let go.' Like, how gnarly is that? I'm stoked. I'm happy to be here."
The Sk8er Boi star last attended the event aged just 18 back in 2003, rocking her signature tomboy look complete with battered Converse and poker-straight hair.
Speaking of her look last night, she told People: "I wore a dress like this in a photo shoot and I was like, 'Oh my God, I love this so much' so we contacted the designer — it's House of MOI MOI — and they custom made this.
"We put Love Sux around the band, that's my album title. And so, I feel like this is just fun tutu vibes ... I feel like so myself right now."