Litvinenko, who had become a Britain-based critic of the Kremlin, became violently ill in November 2006 after drinking tea with two Russian men at a London hotel. He died three weeks later.
Britain has accused Russia of involvement. Moscow denies the claim, and has refused to extradite the two men identified by Britain as the prime suspects.
The inquest's official lawyer, Robin Tam, said that after Litvinenko became sick, a trail of radiation from was discovered across London. Pathologists found he had died from ingesting highly radioactive polonium-210
Judge Robert Owen said has already said that he has seen secret British government material that "established a prima facie case that the Russian state was responsible" for Litvinenko's death.
"The issues to which his death gives rise are of the utmost gravity," Owen said.
The judge said the two Russian suspects - Dmitry Kovtun and ex-KGB agent Alexander Lugovoi - would be invited to give evidence by video link, "an invitation that I hope will be accepted." Both have denied responsibility for Litvinenko's death.
In the opening statement, Tam said speculation about Litvinenko's death had swirled for eight years and that none of the theories has ever been tested in court.
Tam said parts of the saga of Litvinenko's life as a Russian agent and subsequent flight to Britain in 2000 "would not disgrace the pages of a thriller."
He said the inquiry would look at Litvinenko's role in Russia's Chechen war and his later sympathy for the Chechen cause, and would hear evidence that the ex-spy converted to Islam on his deathbed.
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