The Foreign Office said Anna Tsivileva, Putin’s cousin and president of a major mining firm, has been sanctioned.
Vladimir Potanin, Russia’s second richest man and key supporter of Putin’s regime, was also sanctioned on Wednesday due to the war in Ukraine.
The UK government said the sanctions were intended to “weaken the Russian war machine”.
The pair will be subject to asset freezes and travel bans.
Ms Tsivileva, who runs prominent Russian coal mining company JSC Kolmar Group, significantly benefitted from her relationship with the president, the Foreign Office said.
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Oligarch Mr Potanin, owner of major conglomerate Interros, continues to amass wealth supporting Putin’s regime, according to the UK.
He has acquired Russian bank Rosbank and shares in Tinkoff Bank in the period since the invasion of Ukraine.
A UK government spokesperson said: “As long as Putin continues his abhorrent assault on Ukraine, we will use sanctions to weaken the Russian war machine.
“Today’s sanctions show that nothing and no one is off the table, including Putin’s inner circle.”
The sanctions are the latest as part of a series imposed by the UK on Russian individuals and companies.
Foreign Secretary Liz Truss, in Madrid for a Nato summit, told the BBC that Russia must be held to account for its actions.
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