The Serious Fraud Office charges relate to the bank's fundraising at the height of the 2008 financial crisis and a $3bn (£2.3bn) loan to the State of Qatar.
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 and Roger Jenkins each face three charges while Thomas Kalaris and Richard Boath face one apiece.
The charges relate to Barclays' fundraising in 2008, in which the bank raised emergency capital from Qatari investors as the financial crisis sent the sector into meltdown.