Former News International executive Rebekah Brooks and her husband Charlie Brooks have been charged with conspiring to pervert the course of justice.
The charges relate to the police investigation into allegations of media phone hacking and corruption of public officials in Britain. Three of her staff, and News International security head Mark Hanna, are also charged with the offence.
All will appear at Westminster Magistrates' Court on 13 June and have been charged with offences including concealing documents and computers from police, the BBC reports.
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.
"I can't express my anger enough that those closest to me have been dragged into this unfairly," Mrs Brooks, 43, said on Tuesday.
Her husband 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 former News of the World editor herself said she was "baffled" by the decision and described the investigation as a "waste of public money".
"One day the details of this case will emerge and people will see today as nothing more than an expensive sideshow."
Rebekah Brooks was editor of the popular tabloid when voicemails on murdered British schoolgirl Milly Dowler's mobile phone were allegedly intercepted. The paper was also accused of hacking phones of the families of soldiers killed in Iraq and Afghanistan, and relatives of victims of the 2005 London bombings.
Scotland Yard believes up to 4000 people may have had their voicemails accessed.
Mrs Brooks 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, but has denied any knowledge of phone hacking on her watch.