Barclays and four individuals, including former boss John Varley, have been charged with conspiracy to commit fraud relating to the bank's emergency fundraising during the financial crisis.
The Serious Fraud Office (SFO) said it had brought the charges against the bank itself as well as ex-chief executive Mr Varley, 61, Roger Jenkins, also 61, who is the former executive chairman of Investment Banking and Investment Management in the Middle East and North Africa for Barclays Capital, as well as two former senior executives, Thomas Kalaris, 61, and Richard Boath, 58.
The SFO has also charged Barclays plc, Mr Varley and Mr Jenkins with the provision of unlawful financial assistance.
It said the charges relate to the bank's fundraising in 2008, which saw Barclays raise emergency capital from Qatari investors as the financial crisis sent the sector into meltdown.
The SFO charges come after a five-year investigation and centre on the bank's move to raise cash from Qatari investors Qatar Holding and Challenger Universal in June and October 2008, and a 3 billion US dollar (£2.4 billion) loan made available to the State of Qatar in November of that year.
Barclays said it is "considering its position in relation to these developments".
The bank added: "Barclays awaits further details of the charges from the SFO.
"The SFO has informed Barclays that it has not made a decision as to whether it will also bring charges against Barclays Bank Plc in respect of the loan."
The Financial Conduct Authority (FCA) has also reopened its probe into the Qatari fundraising deal and is understood to be reviewing new evidence which could prompt it to reconsider a £50 million fine against the banking giant four years ago.
The emergency funds raised by Barclays allowed it to avoid a government bailout in 2008 at a time when rivals Lloyds Banking Group and Royal Bank of Scotland were forced to rely on a taxpayer rescue.