Ukrainian President Volodymyr Zelenskyy has said Russia is attacking his country's "military infrastructure" and border guards, but urged citizens not to panic and vowed victory.
In a video message posted on Facebook on Thursday, Zelenskyy also introduced martial law across the country, adding that he had spoken by phone with US President Joe Biden.
Meanwhile, the Russian defence ministry confirmed it was targeting Ukrainian military infrastructure with precision weapons.
"Military infrastructure, air defence facilities, military airfields, and aviation of the Armed Forces of Ukraine are being disabled with high-precision weapons," it said in a statement carried by Russian news agencies.
Ukraine will defend itself and will win: Minister
Ukraine's Foreign Minister Dmytro Kuleba accused Russia's Vladimir Putin of launching a "full-scale invasion".
"Putin has just launched a full-scale invasion of Ukraine. Peaceful Ukrainian cities are under strikes," Kuleba tweeted on Thursday.
"This is a war of aggression. Ukraine will defend itself and will win. The world can and must stop Putin. The time to act is now."
Weeks of diplomacy and the imposition of Western sanctions failed to deter Putin, who had massed between 150,000 and 200,000 troops along the borders.
"I have made the decision of a military operation," Putin said in a surprise television announcement that sent global tensions soaring.
Explosions heard in Ukraine capital, other cities
Explosions rang out before dawn on Thursday in Ukraine's capital Kiev and several cities near the frontline and along the country's coasts.
There were blasts in the Black Sea port city of Odessa, close to the frontline of a Russian-backed rebel enclave and just across the sea from Russian-occupied Crimea.
Explosions also rang out in Kharkiv, Ukraine's second-largest city, which lies 35 kilometres (20 miles) south of the Russian border and outside the eastern zone where Kiev.
Closer to the eastern war zone, four loud blasts were heard in Kramatorsk, which serves as the Ukrainian government's effective capital for the eastern war zone.
More blasts rang out in Mariupol, a port on the Sea of Azov which provide a land bridge between Russia and the Kremlin-annexed Crimea peninsula.
Ukraine closes airspace to civilian flights, cites "high risk"
Ukraine said early on Thursday it had closed its airspace to civilian flights because of a "high risk" to safety, hours after a conflict zone monitor warned airlines should stop overflights over the risk of an unintended shootdown or cyber attack.
"The provision of air traffic services to civilian users of the airspace of Ukraine is suspended," Ukrainian State Air Traffic Services Enterprise said on its website.
"We will additionally inform about changes in the use of Ukraine's airspace," the agency added, without providing further details.
Eurocontrol, which coordinates air traffic in Europe, said that Ukraine's airspace was not available because of military restrictions.
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