Police arrested Felicia Boots after her husband Jeff discovered their 10-week-old boy and his 14-month-old sister, Lily Sky Boots unconscious when he arrived home from work last night.
Emergency services were unable to revive the children when they arrived at the semi-detached home in south-west London.
Mrs Boots reportedly had slashed wrists. She is being questioned by police over the deaths.
Detectives suspect she smothered the babies while suffering from post-natal depression.
Mrs Boots, who is in her 30s and is a trained hairdresser, had been busy completing removal from a nearby penthouse apartment in the weeks before the deaths.
Both Mr Boots, an investment banker, and his wife are understood to have moved to the UK in the last few years from Canada.
Forensics teams were today conducting a fingertip search of the property while detectives are carrying out house-to-house inquiries in the affluent area of Wandsworth, South London ? where several homes are valued at £1million.
Post-mortem examinations were due to take place to establish the cause of deaths.
Police said they are not looking for anyone else in connection with the deaths.
A Scotland Yard spokesman said: "Inquiries are underway after the death of two children in Wandsworth.
"Police were called to an address in Killarney Road, Wandsworth, at 7.25pm on Wednesday.
"The ambulance service also attended, but a ten-week-old boy and a one-year-old girl were pronounced dead at the scene."
A London Ambulance Service spokeswoman said: "We were called just before 7.30pm to Killarney Road after reports of an incident.
"Three ambulance crews, and an on-duty officer attended the scene. Two infants were found dead at the scene along with one injured woman. No-one was taken to hospital."
A neighbour, who asked not to be named, said: "My son was coming home last night at about 8.30pm when he was stopped by the police to ask him where he was going."
She added: "The road was sealed off, but he told them he lived here and they allowed him through the cordon.
"There were lots of police, a police van, police cars and an ambulance and this morning there were two people outside the house."
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