The NCA is armed with an annual budget of 463 million pounds to tackle organised crime involving an estimated 37,000 criminals.
The agency will post staff in 120 countries, including Pakistan, and will be more visible than its predecessor, the Serious and Organised Crime Agency.
Over 4,000 NCA officers will tackle crime under four commands - organised crime, economic crime, border policing and child exploitation and online protection - alongside a National Cyber Crime Unit.
The Director General of the NCA, Keith Bristow, issued a stark warning as he took charge: "To be clear, there will be no one beyond the reach of law enforcement or beyond the reach of the NCA.
"Those people involved in the most horrible activities can expect the most comprehensive and robust response."
Bristow said he wanted a different relationship with the private sector to better understand areas of crime like fraud that remain under-reported and under-recorded.
The agency will recruit NCA "specials" - similar to special constables who act as volunteer police officers - with skills in areas like finance to help uncover how some criminals hide their assets.
"We don't want lots of bureaucracy, measuring individual numbers or lots of lines on graphs. We want our officers focussing on cutting serious and organised crime and we'll give the public an insight into the difference we're making," Bristow said.
Proposals for the new agency were first unveiled by Home Secretary Theresa May in July 2010 as part of a broader shake-up of policing.
"I want to make Britain a hostile environment for serious and organised criminals, with the new National Crime Agency leading that fight," she said.
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