Arsala Rahmani was a former Taliban minister and a key member of Afghanistan’s High Peace Council, which leads efforts to negotiate a peace deal with the Taliban.
He was reportedly close to President Hamid Karzai and a key figure in the reconciliation of Taliban commanders.
Last year the peace process was dealt a major blow when the peace council’s chief was killed in a suicide attack.
Burhannudin Rabbani was killed by a bomb hidden in the turban of a suicide attacker posing as a Taliban peace envoy last September.
His US-educated son, Salahuddin Rabbani, was appointed to replace him last month.
Police say that Arsala Rahmani was shot dead by an unidentified gunman in a vehicle, while he was on his way to work in the west of Kabul.
Attackers driving a white Toyota Corolla fired a single bullet using a silencer. Arsala Rahmani reportedly did not have a bodyguard.
Afghanistan’s peace council was set up two years ago by President Hamid Karzai to open negotiations with insurgents.
The council was credited with reconciling hundreds of Taliban field commanders, but had failed to woo any senior figures away from the insurgency.
Arsala Rahmani was responsible for the committee that looked at freeing Taliban prisoners from Bagram and other Afghan prisons.
But how much the peace council achieved in the two years since it was set up remains unclear.
Although the Taliban denied sanctioning last year’s killing of Burhannudin Rabbani, they view the Western-backed Karzai government as illegitimate.
In March the militants suspended parallel preliminary peace negotiations with the United States, saying US efforts to involve the Afghan authorities were a key stumbling block.
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