The 36-year-old actress who arrived minus husband Abhishek Bachchan wore a violet tulle and mousseline gown from Elie Saab.
With her hair done up in a pompadour updo, the actress walked the red carpet with fellow L'oreal spokesmodel, American actress Eva Longoria.
Rai is here to promote her much awaited film, Mani Ratnam's 'Ravan', whose first look will be unveiled on May 17.
Her co-stars including husband Abhishek and Tamil actor Vikram will attend the evening along with the filmmaker.
The bilingual work has been produced by Reliance Big Pictures and is slated for a June release.
The former Miss World, has been a permanent Cannes attendee for many years, since her movie, 'Devdas' screened at the Festival in 2002.
The festival which opened with the premiere of Ridley Scott's 'Robin Hood' was awash with stars including the epic's lead pair Russell Crowe and Cate Blanchett.
Academy Award wining Mexican actress Salma Hayek, who was part of the Festival jury along with India's Nandita Das in 2005, was also present.
British actress Kristin Scott Thomas played mistress of the opening ceremony introducing the President of the jury, American director Tim Burton, and the other members of his team, including India's Shekhar Kapur.
Thomas will also preside over the closing ceremony on May 23, when Burton will announce the prizes.
Indian designers approve Aishwarya's Cannes gown
Indian designers feel that Aishwarya Rai was looking "pretty" and "elegant" in a train gown at the opening ceremony of the Cannes International Film Festival, yet some wished she had stuck to a sari.
The 36-year-old actress had Wednesday night worn a violet blue fully embroidered tulle and mousseline gown from Lebanese designer Elie Saab, teaming it with round solitaires and topped with a buffon hairstyle - reminding one of yesteryears actresses like Sharmila Tagore.
Aishwarya has been attending the French film festival since 2002 as the global face of L'Oreal and except for last year, when she wore a white off-shoulder Roberto Cavalli train gown, the actress had received flak from the designers for her bad dress sense on the red carpet.
This time, Aishwarya got it more right than wrong.
According to designer Vijay Arora the actress looked fabulous on the red carpet.
"The first word that comes to my mind after looking at her picture is Wow! She looked so stunning and ravishing. Also the colour of the gown suited her, " explained Arora.
"Over the period of years, she has learnt the art of mastering the red carpet and she is just getting better day by day, " he added.
Designer Jai from the designer duo Parvesh-Jai too gave a thumbs up to the actress for her growing romance with the gowns at the French film festival.
"Oh, she was looking hot and nice. What a wonderful train gown she was wearing, she just looked stunning. But I was not happy with her hairstyle. The last time, she had pulled it back. This time, she should have tied it in a bun or may be left it open, " Jai explained.
"I guess she looked a bit formal as well..something we don't see in her when she is in India or on any other red-carpet. Maybe it is the French atmosphere that does the trick, " he added.
However, designer Leena Singh of designer duo Ashima-Leena felt that a sari could have been chosen over the gown.
"There is no doubt that she is a beautiful woman and looked elegant in that gown. She projects modern India to the world, so I feel if she could have worn a sari instead, the message could have reached to millions of people that we are modern yet we are Indian at heart, " Leena Singh told.
Designer Charu Parashar agreed, saying that as a style icon, Aishwarya could have done much better.
"You see, that feathery gown did not bring out the real Aishwarya. She could have worn a backless sari and looked very sexy. She is beautiful and her body type is excellent for a sari. I think she could have done much better, " Parashar maintained.
Here, Jai came to Aishwarya's rescue, saying that in all possibility, the final call on the dress code was taken by the sponsors and not her, so the actress should not be blamed.
"Well, it's very easy to say that wear a sari. But the thing is that she is representing India for an international cosmetics brand. So, I am sure that it is a policy decision of the sponsors and not her, " maintained Jai.
"We should spare her for this and appreciate that she has been representing India there for eight years now and every year, she is getting better and better, " he added.