Barclays and four former top bankers, including ex-boss John Varley, have been charged with fraud over side-deals struck during the bank's emergency fundraising at the height of the financial crisis.
The Serious Fraud Office (SFO) said it had brought charges of conspiracy to commit fraud against the bank itself as well as ex-chief executive Mr Varley, Roger Jenkins, Thomas Kalaris and Richard Boath after a five-year investigation into the events surrounding its cash call in 2008.
It marks the first criminal charges to be brought in the UK against a bank and its former executives for activities during the financial crisis.
The SFO said the charges relate to the bank's emergency fundraising from Qatari investors as the group sought to avoid a government bailout amid the banking sector meltdown.
Qatari investors - the state-backed Qatar Holding and Challenger Universal - pumped £6.1 billion into Barclays during two fundraisings in June and October 2008.
In November that year, Barclays agreed to issue a 3 billion US dollar (£2.4 billion) loan made available to the State of Qatar.
The bank, 61-year-old Mr Varley, Mr Jenkins, also 61, and their two former colleagues Mr Kalaris, 61, and Mr Boath, 58, have all been charged with conspiracy to commit fraud over the June 2008 fundraising.
The bank, Mr Varley and Mr Jenkins face the same charge relating to the second fundraising in October 2008, while they have also been charged with providing unlawful financial assistance.
The defendants and a bank representative will appear at Westminster Magistrates' Court on July 3.
Mr Varley, who was chief executive between 2004 and 2011, headed the bank at the time of the fundraising, while Mr Jenkins is also said to have played a key role in orchestrating the deal.
Mr Kalaris used to lead the bank's wealth and investment management division, while Mr Boath was the former European head of financial institutions group at Barclays.
Barclays said it is "considering its position in relation to these developments".
It added: "Barclays awaits further details of the charges from the SFO."
Investigations have focused on two "advisory services agreements" worth £322 million, which Barclays agreed to pay the Qatar Investment Authority, as well as the 3 billion US dollar loan.
The Financial Conduct Authority (FCA) slapped a £50 million penalty on the bank in 2013 after finding it had failed to disclose arrangements and fees it paid to the Qatari investors.
Barclays contested the fine and the challenge was put on hold while the SFO conducted its investigation, but that stay has been lifted.
The FCA has since reopened its probe into the fundraising deal and is understood to be reviewing new evidence.
The FCA said: "We are pleased that this matter, which led to the stay of our own case, is now in the public domain.
"We welcome a fair and transparent hearing on the basis of the charges set out today by the SFO."
Meanwhile, Barclays is facing legal action from financier Amanda Stavely to recoup £700 million in advisory fees from the bank she claims her firm, PCP Partners, is owed relating to the 2008 fundraising, which Barclays is defending.
Law firm RPC also confirmed that following the SFO charges, it is "actively reviewing" the prospects for claims from Barclays shareholders who bought shares in 2008 and suffered losses.
The SFO charges will come as a further headache for current Barclays boss Jes Staley after a series of recent blows, with the chief executive also facing a regulatory investigation into his own conduct after he attempted to identify a whistle-blower.
Mr Jenkins' lawyer, Brad Kaufman of law firm Greenberg Traurig, said: "Mr Jenkins intends to vigorously defend himself against these charges.
"As one might expect in the challenging circumstances of 2008, Mr Jenkins sought and received both internal and external legal advice on all of the matters covered by the accusations levelled today by the SFO."
Mining giant Rio Tinto said Mr Varley had stepped down as a non-executive director on the board with immediate effect.
Mr Varley has been on the Rio board since September 2011 and also chairs the firm's remuneration committee.
Jan du Plessis, chairman of Rio, praised Mr Varley's "outstanding contribution".
He said: "The board holds him in the highest regard and will miss his valuable insight. Personally, I am not only losing a senior independent director, but a close colleague, whose wisdom and support I am going to miss tremendously.
"On behalf of the board I wish John the very best for the future".