Alison Brittain, the boss of Whitbread, has collected the 44th Veuve Clicquot Business Woman Award, with the boss of Divine Chocolate, Sophi Tranchell, named as the runner up.
The finalists were selected by an independent judging panel. Member of the panel and chair of Capgemini, Christine Hodgson, said both women "represent the diverse nature of business today".
Brittain is just one of seven female chief executives in the FTSE 100 in her role at the helm of the UK's largest hospitality company. Whitbread owns seven brands including Costa Coffee and Premier Inn.
Brittain said: “Madame Clicquot was an incredible and inspirational woman, she set the quality standard for an entire industry and was a passionate and spirited pioneer and innovator. I am both honoured and humbled to receive this award and I’m delighted to be following in the footsteps of so many outstanding women.”
The panel said Brittain was a role model for women aiming to reach the top of large organisations. Starting out as a graduate trainee at Barclays, Brittain worked her way up to head up Lloyds Banking Group's retail banking arm, before taking the reins at Whitbread in January 2016.
She follows in the footsteps of the founder of Unruly, Sarah Wood, who picked up the award last year.
Meanwhile, Jude Kelly, the artistic director of Southbank Centre, was crowned the winner of the inaugural Veuve Clicquot Social Purpose Award, to honour businesswomen and female leaders whose organisations are championing social purpose.
Entrepreneur First founder Alice Bentinck won the entrepreneurial New Generation Award.