Dawn raids took place in south London, Essex, Kent and Merseyside following an international police investigation.
If convicted, officers would have dismantled a criminal service that allowed suspected murderers, drug and firearms traffickers and fugitives to evade detection and operate under fake identities worldwide.
A man, 66, who splits his time between Spain, the UK and Ireland, was arrested at his home in Sydenham, south east London, on Monday.
He is suspected of acting as a broker between criminals seeking to buy the passports and crime group members that supplied them.
Nine people believed to be members of the crime group were also detained on suspicion of conspiracy to pervert the course of public justice and making false instruments in NCA raids in Sutton, Sydenham, Rotherhithe, Hackney, Battersea and Hayes in Kent. They are aged between 34 and 71.
Jacque Beer, regional head of investigations at the National Crime Agency, said the operation is one of the most significant of recent times.
She added: ““We believe that this group’s activities has enabled some of the most serious organised criminality in the UK and around the world.
“Today’s operation has dismantled a criminal service that let drug and firearm traffickers, suspected murderers, and fugitives evade detection and operate internationally under false identities.
“It hasn’t just broken up a widespread and deep-rooted criminal conspiracy, it has led to the strengthening of safeguards against criminal exploitation of the UK passport issuing system.”
The morning operation, which involved more than 250 officers, was also supported by the Metropolitan Police and follows a lengthy NCA investigation into the criminal network codenamed Operation Strey.
NCA officers, working closely with the HM Passport Office and the Dutch National Police, had been monitoring the group’s movements.
They have provided intelligence on fraudulently-obtained genuine passports (FOGs) being used by fugitives which has led to arrests across Europe, Dubai, Australia, Thailand and Brazil.
Another suspected client of the group is Michael Moogan, one of the UK’s most wanted fugitives arrested in Dubai in April.
The group is also suspected of providing the passports to members of high-profile Irish and Scottish organised crime groups.
Officers allege the group specialised in (FOGs) – documents which are issued authentically but have been applied for using false information. The result is a seemingly legitimate document, and FOGs are therefore highly sought after by criminals worldwide.
They sourced individuals who were willing to sell their personal details for passport applications. It is believed payments up to £2,000 were made to those willing to provide their identity.
Security Minister Damian Hinds said: “This is a fantastic result and will do significant damage to the serious organised crime groups who want to inflict misery on our shores and around the world.
“The close working between the NCA and Her Majesty’s Passport Office has been at the heart of this hugely successful operation.
“The government is working to make the UK border one of the most effective and secure in the world, which will also support our ambition of dismantling ruthless organised crime groups.”