Mr Kloppers’ retirement will see him replaced by Andrew Mackenzie who is currently head of the company’s base metals business.
Announcing his retirement, Mr Kloppers said the decision was "never going to be easy, however after almost 20 years with BHP Billiton, 12 as a senior executive and nearly six as CEO, I believe now is the right time to pass the leadership baton."
"The board has decided that Andrew is the right person to lead BHP Billiton in a changing global environment," the company said in a statement.
BHP chairman Jac Nasser said Mr Kloppers, who was appointed chief executive just before the financial crisis, had made an "outstanding contribution" to the firm's growth and was leaving BHP "a safer and stronger company".
Announcing his retirement, Mr Kloppers said the decision was "never going to be easy, however after almost 20 years with BHP Billiton, 12 as a senior executive and nearly six as CEO, I believe now is the right time to pass the leadership baton."
Mr Mackenzie has 30 years' experience working in oil and gas, petrochemicals and minerals, and had previously held senior positions at BP and Rio Tinto before joining BHP in 2008.