He becomes the company's second non-executive director from outside the family, joining Joe Scott Plummer, former chairman of Edinburgh-based fund manager Martin Currie.
After a shake-up following the financial crisis, the businesses within the Edinburgh-based group focus on commercial property, energy, and hospitality and tourism within its rural estates.
The Duke said: "Benny's great breadth of experience, combined with a formidable track record and his familiarity with the Scottish scene in particular will be of huge benefit to our family business as it develops in new directions." Mr Higgins said: "It is an honour to be asked to contribute to the ongoing development of the Buccleuch Group, which has such an extraordinary heritage and the promise of a healthy, vibrant future."
Mr Higgins joins Buccleuch after it has undergone a major restructuring overseen by chief executive John Glen, an accountant by training, who conducted a bank refinancing and sold off a number of its peripheral businesses.
The group returned a modest profit of £700,000 in the year to the end of October 31, 2011 after suffering heavy losses during the financial crisis.
A number of group businesses are concerned with the management, maintenance and improvement of the significant heritage of its Scottish estates of Bowhill, Queensberry, Dalkeith and Langholm, as well as Boughton Estate, Northamptonshire. But it has interests as far afield as Sydney, Australia, and Texas in the US.
Mr Higgins has been chief executive of Tesco Bank since 2008.
After the supermarket group bought out Royal Bank of Scotland from their joint venture that year, he has been overseeing the bank's expansion into new product areas, such as mortgages, and its challenge to the established high street lenders.
He started his financial career at Standard Life, followed by RBS, where he rose to become chief executive of its retail banking business, before taking the same post at Halifax Bank of Scotland.
This is his only corporate position outside of Tesco, although he holds a number of industry and Government positions.
Mr Higgins is a member of the Treasury Taskforce on Financial Inclusion, the Scottish Government's Financial Services Advisory Board, the Glasgow Economic Leadership Board and the Commonwealth Games Legacy Board. He is also a director of Scottish Financial Enterprise and is a Prince's Trust Ambassador.
Richard, 10th Duke of Buccleuch and 12th Duke of Queensberry, succeeded his father to the dukedoms in September 2007. He is also president of the National Trust for Scotland.