The video, which could not be independently verified, shows a man with white hair in civilian clothes getting into a car and a voice offscreen naming him as General Mohammed Khalluf, head of logistics, who has defected.
The man speaking in the video says that Khalluf and his family were being escorted out of Syria on Friday.
Al-Arabiya television said that Khalluf defected along with his son, Captain Ezzedine who headed a reconnaissance unit for the Syrian army.
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The Dubai-based news channel also aired part of an interview with Khalluf in which he said he had planned his defection with units of the "Syrian revolution" - insurgents fighting the regime of President Bashar al-Assad.
Activists said they waited before reporting the defection to ensure that Khalluf and his family had crossed safely into neighbouring Jordan.
Since the March 2011 start of the conflict between Assad's regime and rebel forces, dozens of senior army officers including some 40 generals have defected and headed to Turkey.
Former Syrian premier Riad Hijab defected to Jordan in August
