The UK government has banned Indian-born businessmen Ajay, Atul and Rajesh Gupta and their South African associate Salim Essa from travelling to Britain and frozen their assets.
The UK's Foreign office said the Gupta brothers were "at the heart of a long-running process of corruption in South Africa which caused significant damage to its economy".
They have repeatedly denied any wrongdoing.
This is the first time the UK has imposed sanctions for alleged international corruption under a new regime unveiled on Monday.
The UK's Foreign Secretary, Dominic Raab, told MPs these sanctions will "prevent corrupt actors from using the UK as a haven for dirty money".
In total travel bans and asset freezes were imposed on 22 individuals from six countries.
This include a businessman - dubbed Al Cardinal – accused of misappropriating state assets in South Sudan.
What remains unclear is what assets these individuals have in the UK and whether these measures will be enough to stop the flow of dirty money through the UK that Mr Raab admitted was “a honey pot for corrupt actors”.