Ukraine said the missile had targeted the central city of Dnipro, while the Kremlin said it was doing everything possible to avoid a nuclear conflict but did not confirm it had deployed the weapon.
The Russian missile barrage on the industrial city that left two people wounded is the latest escalation since Ukraine fired Western-supplied long-range missiles on Russia.
The Ukrainian air force said in a statement that Russia in the early hours of the morning had launched several types of missiles at Dnipro, targeting critical infrastructure.
"In particular, an intercontinental ballistic missile was launched from the Astrakhan region of the Russian Federation," the statement said.
A source in the Ukrainian air force confirmed to AFP it was the first time such a weapon had been used since Russia invaded in February 2022.
The source added it was "obvious" that the missile, which is designed to carry both conventional and nuclear warheads, did not carry a nuclear charge.
- Kremlin declines comment -
Asked whether Moscow fired the missile, which can hit targets thousands of kilometres away, Kremlin spokesman Dmitry Peskov said he had "nothing to say on this topic."
The Kremlin, however, did claim it was making "maximum effort" to avoid a nuclear conflict after it updated its nuclear doctrine this week.
The new policy allows Moscow to use nuclear weapons against non-nuclear states and Russia said it should be seen as a warning to the West.
"We have stressed in the context of our doctrine that Russia is taking a responsible position to make maximum effort not to allow such a conflict," Peskov added Thursday.
Ukrainian air defence units downed six missiles, the air force said, without elaborating on whether the intercontinental ballistic missile (ICBM) was among those.
The head of the wider region where the city of Dnipro is located said the Russian aerial bombardment had damaged a rehabilitation centre and several homes, as well as an industrial enterprise.
"Two people were wounded -- a 57-year-old man was treated on the scene and a 42-year-old woman was hospitalised," said the official, Sergiy Lysak.
Russia and Ukraine have escalated their use of deadly long-range missiles over recent days since the United States gave permission to use its ATACMS against military targets inside Russia -- a long-standing Ukrainian request.
British media meanwhile reported on Wednesday that Kyiv had launched UK-supplied Storm Shadow missiles at targets in Russia after being given the green light from London.
The defence ministry in Moscow said its air defence systems had downed two Storm Shadows, without saying whether they were downed on Russian territory or in occupied Ukraine.
The missile escalation is coming at a critical moment on the ground for Ukraine, as its defensive lines buckle under mounting Russian pressure across the sprawling front line.
Russia also on Thursday claimed deeper advances in the war-battered Donetsk region, announcing its forces had captured another village close to Kurakhove, closing in on the town after months of steady advances.
Moscow's defence ministry said Russian forces had taken the small village of Dalne, five kilometres (three miles) south of Kurakhove.
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