Syria's deputy oil minister Abdo Hussameddin announced his resignation, saying he no longer wished to serve a "criminal regime", as he became the most senior official to join the opposition.
"I, the engineer Abdo Hussameddin, the deputy oil minister ... announce my defection from the regime and my resignation," he said in a four-minute video posted on social networking site YouTube.
He added that he was "joining the revolution of the people who reject injustice and the brutal campaign of the regime, which is seeking to crush the people's demand for freedom and dignity."
The 57-year-old who is married and has four children, denounced Russia and China for backing President Bashar al-Assad, saying they were not "friends of the Syrian people but partners in the killing of the Syrian people."
He said he had worked for the Syrian government for 33 years and did not wish to end his life "serving a criminal regime".
"That is why I have joined the right path knowing that this regime will burn down my house, hunt down my family and fabricate lies," said Hussameddin, who was appointed deputy oil minister in August 2009.
Appearing in the video in a dark suit and tie, he solemnly advised his colleagues to abandon "this sinking ship" and said he was also resigning from the ruling Baath party.
"I tell this regime which claims to own the land that you have nothing but the footprint of the tank driven by your savagery to kill innocent people," he said.
Hussameddin also advised Assad's minority Alawite sect not to be partners in the killings taking place in Syria as the government seeks to put down a one-year revolt.
Alawites are an offshoot of Shiite Islam. The majority of Syria's population of 23 million is Sunni Muslim.
Rami, an activist who shot the video of Hussameddin and posted it on YouTube, told AFP in Beirut that the opposition had helped arrange the defection.
He said the video was shot on Wednesday and that Hussameddin had now gone underground. He asked that the location of where the video was shot not be disclosed for safety reasons.
According to the Syrian Observatory for Human Rights, almost 8,500 people have died in the brutal government crackdown against the revolt that erupted last March, the majority of them civilians.
The news of the ministerial resignation came hours after US Defence Secretary Leon Panetta said Washington was looking at delivering non-lethal aid to Syria's rebels, hinting at the first direct US assistance to forces seeking Assad's downfall
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