The Financial Times said the process, which could take 12-24 months, was being led by chairman Jac Nasser, citing people familiar with talks.
The report said the search was at a "very preliminary stage".
A BHP spokeswoman steered clear of commenting on the report directly but did say it was important to have a plan in place.
"We are not commenting on the specifics of the story but succession planning for the CEO and senior management team is an ongoing process and one of the most critical tasks of any board," she said in an emailed statement.
"BHP Billiton's board has always ensured that it has a well-integrated, continual succession process in place for our most senior executives.
"This well-established planning process has worked effectively for many years and delivered a track record of smooth succession at the Group Management Committee level."
Only last week, MiningNews columnist Dryblower flagged that changes at the big miners could be on the cards following the resignation of Anglo American CEO Cynthia Carroll.
"While [Kloppers] may see out another year or so his record is suffering from the same blots that affect all chief executives after a long period in power," Dryblower wrote last Monday.
"The charge into US shale gas was Kloppers' biggest mistake but failing to acquire Potash Corporation in Canada was almost as bad, as was messing up the Olympic Dam expansion.
"Of all the issues underpinning an expectation of wholesale chief executive change among the mega-miners it is a combination of the ‘it's time' factor and the outlook change from growth to cost-cutting."
In September, Kloppers advised that he did not wish to be considered for a bonus for the 2012 financial year due to the impairment the company recorded against the carrying value of the Fayetteville shale gas assets it bought from Chesapeake Energy in 2011.
The Remuneration Committee agreed with that decision and also chose not to award him any deferred shares.
Kloppers' base salary of $US2.2 million ($A2.1 million) was also frozen for a year.
BHP's last major leadership change was when Kloppers replaced Chip Goodyear in 2007.
Kloppers' rise to one of the most important jobs in mining began in the petrochemicals of South African energy company Sasol after he completed a PhD in chemical engineering and materials.
After obtaining his MBA from INSEAD in France, he joined McKinsey & Co as a consultant in the Netherlands.
He joined Billiton in 1993 in the company's aluminium business and played a key role in the merger of that company with BHP.
Kloppers was appointed as non-ferrous materials group president and executive director in 2006.
