Barclays PLC and four former executives have been charged with conspiracy to commit fraud and the provision of unlawful financial assistance.
The Serious Fraud Office charges come at the end of a five-year investigation and relate to the bank's fundraising at the height of 2008's financial crisis.
Former chief executive John Varley is one of the four ex-staff who will face Westminster magistrates on 3 July.
Barclays says it is considering its position and awaiting further details.
Mr Varley, former senior investment banker Roger Jenkins, Thomas Kalaris, a former chief executive of Barclays' wealth division, and Richard Boath, the ex-European head of financial institutions, have all been charged with conspiracy to commit fraud in the June 2008 capital raising.
In addition, Mr Varley and Mr Jenkins have also been charged with the same offence in relation to the October 2008 capital raising and with providing unlawful financial assistance.
Mr Jenkins will "vigorously defend" himself against the charges, his lawyer has told Reuters.
"As one might expect in the challenging circumstances of 2008, Mr Jenkins sought and received both internal and external legal advice on each and every topic covered by the SFO's accusations," said Brad Kaufman from American firm Greenberg Traurig.
Mr Varley was one of Britain's leading bankers, having been chief executive at Barclays for six years, and the charges against him will stun the City. He is the first prominent British banker to face criminal charges in the wake of the financial crisis.
Barclays took £7bn from Qatar in 2008, as banks scrambled to avoid nationalisation. The SFO looked into payments made to Qatar at the same time and after the deal, and whether those payments were correctly disclosed, and whether those might have been inducements to Qatar to support the British bank.