Three US citizen fighters were reported missing in Ukraine
Two military veterans fighting for Ukraine were named in reports this week as having been taken prisoner.
The state department said on Thursday: "There are reports of one additional American whose whereabouts are unknown."
Last week, three foreign prisoners were condemned to death for helping Ukraine.
Two British men and one Moroccan man were sentenced by a Russian-backed separatist court in Donetsk to be executed by firing squad.
The White House said on Thursday it is "working very hard to learn more" about the unverified reports of missing or captured Americans in Ukraine.
A group of former US and French service members tweeted Wednesday that two Americans fighting with them had been captured a week ago.
If the report were confirmed, these would be the first Americans fighting for Ukraine captured since the war began in February.
According to US media, Andy Tai Ngoc Huynh, 27, and Alexander Drueke, 39, had travelled from Alabama to join a Ukrainian volunteer unit.
Alabama congressman Robert Aderholt released a statement on Wednesday saying Mr Huynh, a former US Marine, had "volunteered to go fight with the Ukrainian Army in their current war against Russia".
He added that Mr Huynh's family had not been in contact with him since 8 June 2022, when he was in the Kharkiv area.
The state department said it was looking into claims that Russian or Russian-backed separatist forces in Ukraine had captured two Americans.
But spokesman Ned Price told reporters on Thursday the US "has not raised this yet with the Russian Federation" because Washington does not yet have "credible reason" to believe the Russians have captured the men.
Mr Drueke's mother, Bunny, News that the family has not received confirmation that he has been captured. However, a post by Russian forces on social media claimed that two Americans had been arrested on the same day they went missing.
"As a mother, you want to keep your children safe," she said. "As an American, I am so darn proud of him for being willing to risk his safety to help democracy worldwide."
Mr Huynh's fiancée, Joy Black, said her partner "just had such a burden on his heart to go and help these people in need".
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