Major-General Abdul Aziz Jassem al-Shallal headed the country's military police and is one of the highest military officers to defect from the Assad regime.
Jassem al-Shallal announced his defection over the Egypt-based Al Arabiya television and his move came as Opposition fighters continued to gain ground in battles against regime forces across the country.
The Syrian General was reported to be near the Turkish-Syrian border and said that there were other high-ranking officers who were planning to defect.
Jassem al-Shallal claimed that Assad's men were keeping a close tab on the army.
Al Arabiya said more than a dozen generals have defected since the Syrian crisis began in March 2011.