Rihanna was seen strolling through the Palace's luxurious rooms during the late night shoot, while wearing a glamorous sequin gown - and a pair of fluffy slippers.
Her thick hair was styled in luxurious waves, swept back off her face to allow her features to shine, while a bold dark lipstick spiced up the look.
Rihanna posed among a hallway of gold statues as cameras flashed away.
Earlier that day, the star was also seen enjoying some downtime in her trailer, which was located at the Palace.
Rihanna was pictured lying down, while having her nails done by an assistant.
This new campaign will mark Rihanna's debut as a model for the brand - however she is known to be a great fan, and is often seen wearing a variety of Dior's latest and greatest designs while frequently featuring on the front row at the label's Paris Fashion Week catwalk shows.
Rihanna boasts plenty of fashion experience, having previously modeled for the likes of Balmain and Emporio Armani, as well as appearing on numerous covers of fashion bible Vogue.
She joins the likes of Hunger Games star Jennifer Lawrence, Black Swan actress Natalie Portman and French beauty Marion Cotillard, all of whom have starred in campaigns for Dior in the past.
The last installment of the Secret Garden campaign, which debuted in May 2014, has had more than nine million views on YouTube. It was also shot at the iconic French palace.
Making clear the key role that the historical setting plays within the campaign, Dior said of its previous video installment: "As the eyes open upon the famed perspective of the chateau gardens and their massive geometries, as on the cusp of a dream, the Dior woman draws the spectator with her around the twists and turns of a secret and amazing Versailles."
Known also as the Chateau de Versailles, the extravagant royal residence is located just southwest of Paris.
Three French kings lived there, including Louis XIII, Louis XIV, and Louis XV, up until the French revolution in 1789.
Each king increased the palace's splendour by continuing to build upon the premises.
- Daily Mail