Russian forces have invaded Ukraine by land, air and sea, confirming the worst fears of the West with the biggest attack by one state against another in Europe since World War II.
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Russian missiles rained down on Ukrainian cities.
Ukraine reported columns of troops pouring across its borders into the eastern Chernihiv, Kharkiv and Luhansk regions, and landing by sea at the port cities of Odessa and Mariupol in the south.
Explosions could be heard before dawn in the capital Kyiv. Gunfire rattled, sirens blared across the city and the highway out became choked with traffic as residents tried to flee.
Ukraine's President Volodymur Zelenskiy said Kremlin leader Vladimir Putin's aim was to destroy his state.
EU foreign affairs chief Josep Borrell said: "These are among the darkest hours of Europe since the Second World War."
Initial reports of casualties were sporadic and unconfirmed. Ukraine reported at least eight people killed by Russian shelling and three border guards killed in the southern Kherson region.
Ukraine's military said it had destroyed four Russian tanks on a road near Kharkiv, killed 50 troops near a town in Luhansk region and downed six Russian warplanes in the east.
Russia denied reports that its aircraft or armoured vehicles had been destroyed. Russian-backed separatists claimed to have downed two Ukrainian planes.
In a televised declaration of war in the early hours, Putin said he had ordered "a special military operation" to protect people, including Russian citizens, subjected to "genocide" in Ukraine, an accusation the West calls absurd propaganda.
"And for this we will strive for the demilitarisation and denazification of Ukraine," Putin said.
"Russia cannot feel safe, develop, and exist with a constant threat emanating from the territory of modern Ukraine...All responsibility for bloodshed will be on the conscience of the ruling regime in Ukraine."
US President Joe Biden said his prayers were with the people of Ukraine "as they suffer an unprovoked and unjustified attack". He promised tough sanctions in response, and said he would swiftly consult with other world leaders.
The prospect of war and sanctions disrupting energy and commodities markets posed an immediate threat to a global economy barely emerging from the pandemic. Stocks and bond yields plunged, while the dollar and gold rocketed higher. Brent oil surged past $US100/barrel for the first time since 2014.
Ukraine, a democratic country of 44 million people, voted overwhelmingly for independence after the fall of the Soviet Union, and aims to join NATO and the European Union, aspirations that infuriate Moscow.
Putin, who denied for months that he was planning an invasion, has called Ukraine an artificial creation carved from Russia by its enemies.
Three hours after Putin gave his order, Russia's defence ministry said it had taken out military infrastructure at Ukrainian air bases and degraded its air defences.
Earlier, Ukrainian media reported that military command centres in Kyiv and Kharkiv in the northeast had been struck by missiles, while Russian troops had landed in the southern port cities of Odessa and Mariupol.
Queues of people waited to withdraw money and buy supplies of food and water in Kyiv. Traffic was jammed going west out of the city of three million people, towards the distant Polish border. Western countries have been preparing for the likelihood of hundreds of thousands of Ukrainians fleeing an assault.
Biden said Putin had chosen a premeditated war that would bring a catastrophic loss of life and human suffering.
"Russia alone is responsible for the death and destruction this attack will bring, and the United States and its Allies and partners will respond in a united and decisive way," said Biden, who spoke to Zelenskiy by telephone.
NATO Secretary-General Jens Stoltenberg said NATO allies would meet to tackle the consequences of Russia's "reckless and unprovoked attack".
British Prime Minister Boris Johnson said Putin had chosen "the path of bloodshed and destruction".
China, which signed a friendship treaty with Russia three weeks ago, reiterated a call for all parties to exercise restraint and rejected a description of Russia's action as an invasion.
Australian Associated Press
