Chinese espionage is a politically sensitive subject in Britain and the case could potentially become awkward for Starmer who visited Beijing recently as part of his resetting of relations with the Asian giant.
The trio, aged 39, 43 and 68, were arrested by counter-terrorism officers in London and Wales on suspicion of assisting a foreign intelligence service, London's Metropolitan police said.
"I have never seen anything to make me suspect my husband has broken any law," said MP Joani Reid after UK media reported that her husband David Taylor was among those arrested.
"I am not part of my husband's business activities and neither I nor my children are part of this investigation," she added.
All three men remain in custody and the arrests come amid rising concerns over alleged Chinese espionage in the UK.
Starmer has been criticised by opposition politicians, human rights groups and US President Donald Trump for greenlighting a massive new Chinese embassy in central London and for visiting Beijing earlier this year.
The UK leader has repeatedly defended his visit to China, the first by a British prime minister since 2018, as important to forge closer ties with the world's second largest economy.
Reid, who represents a constituency in Scotland and sits on parliament's Home Affairs Select Committee, defended herself against any potential accusations of her being close to Beijing.
"I have never been to China," she said. "I have never spoken on China or China-related matters in the Commons. I have never asked a question on China-related matters."
Taylor, 39, is listed as a "lobbyist" on Reid's list of registered interests. According to his LinkedIn page, he works for Asia House, a think tank.
- 'Severe consequences' warning -
Earlier, security minister Dan Jarvis told MPs the UK had made diplomatic representations to China over the matter.
"If there is proven evidence of attempts by China to interfere with UK sovereign affairs, we will impose severe consequences and hold all actors involved to account," he said.
"We remain deeply concerned by an increasing pattern of covert activity from Chinese state linked actors targeting UK democracy," Jarvis added.
The speaker of the House of Commons lower chamber told MPs that Reid's husband, "did not have a pass to access the parliamentary estate".
Britain's domestic spy agency MI5 warned in November that China was attempting to "cultivate individuals" with access to sensitive information about parliament and the UK government.
Last year, legal proceedings against two men accused of spying for China, one of whom had been a parliamentary researcher, collapsed, sparking a political row.
Helen Flanagan, head of Counter Terrorism Policing London at the Met, said Wednesday that the force had seen "a significant increase in our casework relating to national security in recent years".
Opposition Conservative party leader Kemi Badenoch said "the government needs to stop being naive, grow a backbone and treat China as the threat we all know it is".
A spokesperson for China's embassy in London said "some people in the UK are always keen to fabricate facts and concoct so-called 'espionage cases' to maliciously slander China".
"We urge the relevant British parties to immediately cease such anti-China political manipulation."
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