The 48-year-old star looked incredible in the glamorous gown, which featured a plunging neckline and thigh-high split.
The open-backed dress also showed off her hourglass figure with a clinched-in waist.
Celine topped the outfit off with a diamond-studded green belt and matching shoes.
This year's ceremony came one year after Celine's husband, Rene Angelil, died following a battle with throat cancer.
Celine Dion takes the plunge in emerald dress as she opens up about late husband
Celine wowed in her emerald dress with matching shoes and belt
The back of Celine's dress was equally as stunning
Grammys 2017: WORST dressed
Mon, February 13, 2017
Here are the most the WORST DRESSED from this year's Grammys.
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Grammys 2017: Worst dressed
I will never forget sitting with my husband Rene when 'My Heart Will Go On' won the Grammy Award for Song of the Year 18 years ago
As the singer donned a figure-hugging black dress to present the Song of the Year award, she opened up about her late husband.
"Stevie Wonder once said, 'Music, at its essence, is what gives us memories'," she told the star studded audience.
She continued: "I will never forget sitting with my husband Rene when 'My Heart Will Go On' won the Grammy Award for Song of the Year 18 years ago."
It was then that the crowd erupted into applause and Celine thanked them for their support.
The singer chose to pair simple earrings with the stunning dress
Celine wore a black dress as she presented an award during the show
Earlier on the red carpet, Celine revealed more about how she is coping with his passing, saying: "We're doing really well, thank you for asking.
"There's days where I feel it's been three years and then there's days it feels like it's not happening. He's always with me and I know that he's very proud," she continued.
Celine also interrupted an interview as Lady Gaga passed to congratulate her about her recent Super Bowl performance, saying: "Congratulations on the Super Bowl, you're amazing. I love you!"
Another memorable moment on the night saw Adele reduce Beyonce to tears as she collected the gong for Album of the Year.