As the Taleban's only foreign envoy, the 34-year-old ambassador to Pakistan quickly became the international face of the regime under fire.
The only other two countries which had recognised the Taleban, Saudi Arabia and the UAE, had sent their Afghan diplomats home as the pressure to isolate the regime intensified.
Accompanied by a stern one-eyed translator with a plastic hand, Mullah Zaeef gave daily press briefings to the media while bombs dropped on his homeland, and was frequently seen smiling and joking with journalists.
From the outset the bespectacled mullah insisted that the US retaliatory campaign against Afghanistan was an unjust one, and said his country would fight to protect the "dignity of Islam".
He also provided graphic details of the casualties and suffering he said had been inflicted during the intensive raids.
It was Mullah Zaeef's popular briefings that prompted an anxious US and UK to set up a media centre in Pakistan to improve their propaganda campaign, fearing they were losing the public relations battle.
Game over
Mr Zaeef's official appearances continued until the Pakistani authorities, who had already sought to rein in his briefings, decided to close down his embassy in late November, severing ties with a regime they had traditionally sponsored.
But seen by many as representing the more moderate side of his fundamentalist colleagues, there was initially some suggestion that he might be included in an interim government to replace the old regime.
Such ideas were rejected. Afraid for the safety of himself and his family, comprised of two wives and six children, he applied for asylum in Pakistan, but his application was turned down.
On 5 January, Mr Zaeef was deported to Afghanistan, where he was taken into custody by US military forces.