Following in the footsteps of Jennifer Lopez, Angelina Jolie and Keith Richards, the legendary fighter takes centre stage in the company's new promo shoot, which was snapped by celebrated photographer Annie Leibovitz at the star's home in Arizona.
Ali and one of his grandsons are seen wearing a pair of boxing gloves in the image.
"Muhammad Ali is the epitome of an outstanding personality - a true living legend in boxing and far beyond. We are honoured that he agreed to be photographed for the Core Values campaign, and delighted with the way this beautiful portrait of the champion and his grandson captures the idea of transmission," said Yves Carcelle, Chairman of Louis Vuitton.