The UN’s updated sanctions list named the four as Omar Hussain from High Wycombe, Nasser Muthana from Cardiff, Aqsa Mahmood from Glasgow and Sally-Anne Jones from Chatham, in Kent.
They will face a travel ban and a freeze of their assets.
The move is a new tactic to stem the flow of recruits to the IS group.
At least 700 Britons have travelled to support or fight for jihadist groups in Syria and Iraq, according to British police. About half have since returned to the UK.
A government official said it was the first time in 10 years that Britain had submitted names to the UN’s sanctions list and the move was intended to send out a deterrent message.
One name submitted to the sanctions committee is still to be approved.
More are expected to be put forward.
Dossiers of evidence were submitted to show the Britons were “participating in the financing, planning, facilitating, preparing, or perpetrating of acts or activities” related to IS.
Uploading bomb-making instructions to social media was among the activities.
The UN sanctions regime was set up to tackle suspected al-Qaeda terrorism and was extended to IS.
The government official said: “We will absolutely go after people who fight for ISIL and are threatening our country.”
The four named by the government have been widely reported by the British media for their alleged activities with the IS group.
- Aqsa Mahmood, 21, has been accused of recruiting three London schoolgirls to join the IS group – something her parents have denied.
- Nasser Muthana, 21, is accused of appearing in videos showing beheadings,although his father said it was not him.
- Sally-Anne Jones, 46, – reportedly a former rock musician – has been dubbed the “punk jihadi” by the tabloid newspapers and is accused of recruiting for the group.
- Omar Hussain, 28, a former supermarket security guard, has appeared in a propaganda video and was interviewed on Newsnight.
Aqsa Mahmood travelled to Syria in 2013 and is believed to have married a fighter in the IS group.
She is described on the list as being a recruiter for the militant group and a key figure in the al-Khanssaa brigade – a female brigade within IS, established in the Syrian city of Raqqa to enforce its interpretation of Sharia law.
Nasser Muthana and Omar Hussain travelled to Syria in 2013 and 2014 respectively and are both described as fighters for IS.
Sally-Anne Jones, who was married to Junaid Hussain, a British jihadist killed in a Syria drone strike, travelled to Syria with her husband in 2013 and is on the list for being a recruiter for the group.
The announcement of the sanctions comes as the prime minister joins other world leaders at the UN General Assembly in New York.
The government is also to spend an extra £10m on a new unit to counter propaganda from IS militants and is establishing a new committee of senior ministers to focus on the threat from the group.
A British official said Prime Minister David Cameron believes “we can and must do more to win the battle for hearts and minds”.
The new unit will be based in London but with links across the Arab world to try to counter the extremist message.
Three British nationals were already among the 231 individuals and 72 organisations on the UN list.
Earlier this month, it emerged that two British Islamic State fighters had been killed by an RAF drone strike in Syria.
Cardiff-born Reyaad Khan, 21, and Ruhul Amin, 26, from Aberdeen, died in Raqqa in August, alongside another fighter.
Khan, who was the target, had been plotting to attack “high-profile public commemorations” taking place in the UK this summer, the prime minster said.