The large, five-door family hatchback is the third, and most upmarket, of the premium DS Line and to coincide with its UK launch, it was called into action at the prestigious film awards in London.
Stars such as TV personality Jonathan Ross, Harry Potter actress Bonnie Wright and award-winner Olivia Coleman all arrived in the back of the five-seat Citroens before walking down the red carpet.
The Citroen DS5 is unlike most executive cars because it comes with dramatic styling including a coupe-like roofline, aggressive front end decked out with LED lights, chrome highlights and a large grille.
Designed to sit somewhere between an estate and a large hatchback, the Citroen DS5 comes with a choice of equipment-packed trim levels and, under the bonnet, diesel, petrol and a unique hybrid engine option.
The headline-grabbing Hybrid4 engine is a diesel-electric engine first seen in the Peugeot 3008 HYbrid4 crossover.
Using a mixture of electric power and a diesel engine, the Citroen DS5 HYbrid4 delivers 200bhp and four-wheel drive.
It also comes with low running costs with HYbrid4 versions emitting just 99g/km of CO2 emissions and qualifying for free road tax and exemption from the London congestion charge in the process.
New Citroen DS5 prices start from £23,000 and rise to around £33,000 in the UK and the Citroen DS5 is on sale now from Citroen dealerships.
It is the third model in the new DS range from Citroen after the successful introduction of the new Citroen DS3 supermini and the Citroen DS4 hatchback.