Maher Rahhal, who headed the Liwa al-Mujahideen Brigade, one of the groups fighting the forces of Syrian President Bashar al-Assad, "was shot twice in Abu Nseir district" in Amman late Friday, the official said.
"Security services have formed a special team to investigate the crime," the official told AFP, ruling out however that the murder was politically motivated.
"There is no indication that the crime was a political assassination."
The opposition Syrian National Coalition condemned the killing in a statement posted on its official website, and said it holds the Assad government "responsible for this crime."
Jordan, home to more than 600,000 Syrian refugees, has been accused by the government in Damascus of supporting the rebels - a claim denied by Amman.
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