Following a board meeting on Wednesday, the consumer goods giant said that it intends to "simplify" from two legal entities into a single one incorporated in the Netherlands.
"The proposed simplification will provide greater flexibility for strategic portfolio change and help drive long-term performance," the group said.
Unilever insisted that its 7,300 workers the UK and 3,100 in the Netherlands will be unaffected by the changes.
It added that Unilever will continue to be listed in London, Amsterdam and New York.
The announcement comes after a review of Unilever's dual-headed legal structure in the UK and Netherlands, which was part of a rethink of the business following a hostile takeover attempt by Kraft Heinz last year.
Unilever, which is behind well-known household brands such as Dove, Marmite and Ben & Jerry's ice cream, employs around 169,000 people around the world.
However, the company has not broken down figures showing the number of staff involved in its headquarters operations in London.
The decision is likely to cause further embarrassment for the Conservatives and Prime Minister Theresa May, who is struggling to contain a flow of businesses and their staff to the EU.
British Government officials reportedly met with Unilever to express their concerns that the London headquarters would be axed in favour of the Netherlands, but failed to convince them over the benefits of basing its main offices in the UK.
The Government is already under fire for failing to provide adequate assurances to businesses mulling their post-Brexit futures, particularly in light of plans to leave the EU single market.
But a Government spokesperson said: "Unilever has today shown its long-term commitment to the UK by choosing to locate its two fastest-growing global business divisions in this country, safeguarding 7,300 jobs and £1bn a year of investment.
"As the company itself has made clear, its decision to transfer a small number of jobs to a corporate HQ in the Netherlands is part of a long-term restructuring of the company and is not connected to the UK's departure from the EU."
As part of the rejig, Unilever will also restructure into three divisions - beauty and personal care, home care, and foods and refreshment - which will each have different headquarters split between the UK and the Netherlands.
The beauty and personal care, and the home care divisions will be headquartered in London, while the foods and refreshment arm will have its HQ in Rotterdam.
Unilever chairman Marijn Dekkers said: "Our decision to headquarter the divisions in the UK and the Netherlands underscores our long-term commitment to both countries.
"The changes announced today also further strengthen Unilever's corporate governance, creating for the first time in our history a 'one share, one vote' principle for all our shareholders."