A police spokesman said five shots hit an armoured vehicle of the Organisation for Security and Cooperation in Europe (OSCE) in the windscreen.
The boundary zone remains tense after a five-day war in August, when Russia sent in tanks and troops to repel a Georgian assault on the rebel capital Tskhinvali.
An OSCE spokeswoman confirmed the incident.
"A firing incident has taken place involving an unarmed OSCE monitoring patrol," the spokeswoman told Reuters. "The full details are being looked into."
Neither the police nor the OSCE could specify where precisely the incident took place, but the police said it was "close to the de facto border" between Georgia and South Ossetia.
A small OSCE mission has monitored the region since South Ossetia broke away from Tbilisi's rule in the early 1990s. The European Union also has some 225 unarmed observers patrolling the boundary zone, deployed under a ceasefire brokered by France after the August war.
There are frequent reports of ceasefire violations, usually involving Georgian police and South Ossetian security forces trading fire.
Neither monitoring mission has been allowed to enter South Ossetian territory since the August conflict.
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