The operation led to the safeguarding of 400 children and has resulted in charges brought ranging from possessing indecent images of children to serious sexual assault, it said in a statement.
Some 45 police forces across England, Scotland, Wales and Northern Ireland were involved in the operation.
Britain has been rocked by a series of paedophile scandals in the last two years, since revelations that late BBC television host Jimmy Savile was a serial sex offender.
The NCA stressed that none of those arrested in the operation is a serving or former lawmaker or member of the government.
"This is the first time the UK has had the capability to coordinate a single targeted operation of this nature," said NCA Deputy Director General Phil Gormley.