The blast seems to have been timed to coincide with the precise moment that policing and justice powers devolved from Westminster to Stormont.
It happened at about 0020 BST outside Palace Barracks, where MI5 has its NI headquarters. A warning was given.
The Real IRA has admitted the attack. An elderly man was treated in hospital for minor injuries.
The bomb was placed in a taxi, which was hijacked in the Ligoniel area of north Belfast, about seven miles from Holywood, at about 2150 BST.
The driver was held hostage by three men for about two hours before being told to drive his taxi to the barracks.
Security staff began evacuating the area just before midnight and the bomb exploded at about 0020 BST.
There were two explosions - first the bomb and then the petrol tank, destroying the car and damaging other property. An elderly man walking near the barracks at the time of the explosion was treated in hospital for minor injuries.
Police were still evacuating the surrounding area when the bomb went off.
Up to 60 people were moved from their homes and spent the night in a community centre.
The attack appears to have been timed to coincide with the transfer of policing and justice powers from London to Belfast.
Northern Ireland Secretary Shaun Woodward said this "democratic transition stands in stark contrast to the activity of a criminal few who will not accept the will of the majority of people of Northern Ireland".
"They have no support anywhere," he added.
Justice transfer
In March, Northern Ireland Assembly members voted in favour of the transfer of policing and justice powers. Out of the 105 votes cast in the Assembly, a total of 88 supported the move, with 17 Ulster Unionists voting against.
Disagreement on the timing of the devolution of the justice powers had threatened to collapse Northern Ireland's power-sharing administration.
Later on Monday, Stormont assembly members are due to vote to appoint a new justice minister - the first Northern Ireland politician to take responsibility for justice and policing in 38 years.
The man expected to get the job is David Ford, the leader of the cross-community Alliance Party.
His department will take over responsibility for many functions and agencies previously controlled by the London-based Northern Ireland Office.
As well as taking over responsibility for the police, the new ministry will oversee bodies like the Northern Ireland Prison Service, the prosecution service, the Probation Board and the forensic science service.