Sergei Skripal, 66, who moved to Britain in a 2010 spy swap, is in a critical condition in hospital along with his daughter Yulia after they collapsed on a bench outside a shopping centre on Sunday.
The brazen poisoning in the southwestern English city of Salisbury is already being linked with Russia by British politicians and the media, sparking an angry response in Moscow.
"Sadly, in addition, a police officer, who was one of the first to attend the scene is now also in a serious condition in hospital," Metropolitan Police assistant commissioner Mark Rowley told reporters.
Scientific tests by government experts have identified the specific nerve agent used "which will help identify the source", he added, declining to reveal the exact substance.
British media reports suggest the three victims are seriously ill.
Britain's Sky News, quoting sources, said all three victims are in a coma. The Times newspaper, quoting a senior unnamed British government official, said Skripal's condition was thought to be particularly severe.
The paper added that the police officer's condition was thought to be "less severe".
Other emergency services personnel who treated the pair required medical treatment at the time but have not been admitted to hospital.
Interior minister Amber Rudd called for "cool heads" over the poisoning amid swirling speculation.
Police say they are keeping an open mind about what happened, but Foreign Secretary Boris Johnson has alluded to Russia.
Moscow accused British politicians and journalists of whipping up anti-Russian sentiment, with Kremlin foreign ministry spokeswoman Maria Zakharova telling reporters the story "was straight away used to boost an anti-Russian campaign in the media".
Zakharova earlier said Johnson's comments were "wild".
Meanwhile, hundreds of counter-terrorism detectives are working "around the clock" to create a timeline of the victims' movements, with "many hours" of CCTV under review, police said.
Investigators believe Skripal and his 33-year-old daughter were in Salisbury city centre for several hours before they were found slumped on a bench.
An anonymous witness who was in the pub, which has been closed by police, told the BBC yesterday that Skripal was there behaving erratically and at one point shouting loudly.
Rowley appealed for information from those in Salisbury on Sunday.
"Your memory of that afternoon and your movements alone could help us with missing pieces of the investigation," he said.
The Times reported police are probing whether Skripal's daughter, who arrived in Britain from Moscow last week with "gifts from friends", may have inadvertently brought the nerve agent into the country.
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