Rebekah Brooks and her husband, Charlie, have been charged with conspiracy to pervert the course of justice over the phone-hacking inquiry.
Three of Mrs Brooks’s staff, and News International security head Mark Hanna, are also charged with the offence.
Mrs Brooks said: “I can’t express my anger enough that those closest to me have been dragged into this unfairly.”
They will appear at Westminster Magistrates’ Court on 13 June.
They have been charged with offences including concealing documents and computers from police.
The charges, which relate to alleged offences in July last year, are the first in an inquiry lasting 18 months – more than 40 other people remain on police bail in the investigation.
Mr Brooks said he had been used as a “scapegoat” to “ratchet up the pressure” on his wife, who he claimed was the victim of a “witch-hunt”.
The ex-News of the World editor herself said she was “baffled” by the decision.
She described the investigation as a “waste of public money” and added: “One day the details of this case will emerge and people will see today as nothing more than an expensive sideshow.”
Mrs Brooks was editor of the News of the World (NoW) when voicemails on murdered schoolgirl Milly Dowler’s mobile phone were allegedly intercepted.
She quit as chief executive of News International in July 2011 – the same month as the alleged conspiracy offences – after the phone-hacking scandal led to the paper’s closure.
Mrs Brooks, 43, from Churchill, Oxfordshire, has denied any knowledge of phone hacking on her watch.
Announcing the decision to charge the six, the director of public prosecutions’ senior legal adviser Alison Levitt, QC, said she was making a statement “in the interests of transparency and accountability”.
Mrs Brooks was arrested on 13 March as part of Operation Weeting.
She is charged with conspiring with her 49-year-old husband, personal assistant Cheryl Carter, chauffeur Paul Edwards, security man Daryl Jorsling, and News International head of security Mr Hanna to “conceal material” from police between 6 and 19 July.
In a second charge Mrs Brooks and Ms Carter are accused of conspiring to remove seven boxes of material from the News International archive between 6 and 9 July.
In a third charge, Mr and Mrs Brooks, Mr Hanna, Mr Edwards and Mr Jorsling are accused of conspiring to conceal documents, computers and other electronic equipment from police officers between 15 and 19 July.
A seventh unnamed suspect, who also provided security for Mrs Brooks, will not be charged.
Lawyer Henri Brandman said Ms Carter, 48, from Chelmsford, Essex, “vigorously” denied the charge she faces and thanked her family and friends for their support during this “most unhappy period of her life”.
Mr Hanna said he would be “totally exonerated”, adding that he was innocent of the charges against him and he had “no doubt that ultimately justice will prevail”.
Mrs Brooks became editor of the NoW in 2000 at the age of 31 before she took up the same role at the Sun three years later.
Racehorse trainer Charlie Brooks, Mrs Brooks’s husband, faces charges
She was made chief executive of News International in 2009 and resigned in July 2011.
She was arrested a few days later on suspicion of conspiring to intercept communications and corruption, and remains on bail without charge for those alleged offences.
Mrs Brooks was then re-arrested on 13 March on suspicion of conspiring to pervert the course.
On Friday, appearing at the Leveson Inquiry into press ethics, Mrs Brooks said that Prime Minister David Cameron sent her a “keep your head up” message when she quit News International.
The BBC’s June Kelly said the developments were likely to be “highly embarrassing” for Mr Cameron who attended Eton College with Mr Brooks and was a friend of both the racehorse trainer and his wife.
Our correspondent said of Mrs Brooks: “For a decade she was close to those at top of Scotland Yard but for the past year the force, which once loaned her a horse, has been investigating her.
“The woman who, for so long, wielded power and influence in British public life must now begin preparing for her first court appearance.”
Mr Jorsling, 39, from Ash Vale, near Guildford, Surrey; Mr Edwards, 47, of Kilburn, west London; and Mr Hanna, 49, from Buckingham, Bucks, were all notified of the charges on Tuesday.
Scotland Yard is conducting three investigations relating to phone-hacking.
Operation Weeting is looking into allegations of hacking by the NoW into private voicemails, Operation Elveden is examining allegations that journalists from News International made “inappropriate” payments to police, and Operation Tuleta is investigating computer hacking.