The Tasmania-born princess wore her glossy brown locks in an elegant chignon, revealing a set of glittering diamond and sapphire earrings.
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Prince Frederik, who matched his wife of ten years in a midnight blue suit, looked on proudly as she took to the stage to collect a Bambi Award for her charity work, and in particular her focus on domestic violence.
As she made her way back to her seat, mother-of-four Mary lost her footing and almost took a tumble but managed to regain her balance and share a smile of relief to those around her.
The awards, now in their 66th year, are held to honour excellence in international media and television.
Also being recognised for their work on Wednesday evening were Kill Bill star Uma Thurman, who was named Best International Actress, and U2, who took the accolade for Best International Music Act.
The Irish rockers treated the crowd to a live performance, which included tracks from their new album Songs of Innocence.
German tenor Jonas Kaufmann, piano virtuoso Lang Lang and Break Free singer Ariana Grande were also awarded Bambis.