Hours before her flawless appearance at the star-studded event, the Russian beauty confirmed she was expecting her first baby with Antoine Arnault.
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With that in mind, all eyes were on Natalia's petite frame as she arrived at the Claridge's Hotel for the ceremony. At just three months pregnant — the new arrival is due in May — she showed just the tiniest hint of a baby bump beneath her floor length gown.
Natalia, 31, was named winner of the Philanthropist award for her work for the Naked Heart Foundation, which she established in 2005 to ensure every child in Russia has a loving family and safe place to play.
That honour, combined with her pregnancy joy, ensured the mum-of-three had a night to remember.
It was Natalia's proud partner Antoine Arnault who first revealed she was expecting her fourth child.
Antoine, the son of LVMH chairman Bernard Arnault and CEO of luxury brand Berluti, made the big announcement on Facebook on Tuesday morning.
"Hi everyone, big news today!," he wrote, posting six touching images of the happy couple. "Giving a little brother or sister to Natalia's 3 wonderful children is something we wanted so much: AND NOW IT'S HAPPENING! :)))
We're going to have out first baby next year!!! #4 for her but #1 for me… I'm a little stressed! She was tired the first 3 months but is fine now…
"I hope he or she gets Mommy's looks (and beautiful heart!!!) and Daddy's sense of humour!! Pleaaaase not the other way round!!! :)))"
His supermodel girlfriend shared the post, adding a few words of her own.
"Please read cute post by future daddy and share our big news," she wrote. "This will explain to many of my friends and colleagues why I have been cancelling on them so often recently…
"We are due in May and all the family is very excited to welcome in a new little member."
Natalia and 36-year-old Antoine started dating in 2011. The Russian supermodel has three children from her marriage to British property heir Justin Portman; Lucas, 11, Neva, seven and Viktor, six.