The Independent Police Complaints Commission (IPCC) are to look into contact between police and two people found shot in Newport on Thursday.
A 46-year-old woman died and a 49-year-old man is in a critical condition in hospital after the incident.
Police said they were not looking for anyone else.
Investigations are continuing. Police have now said it involved an estranged couple.
Armed officers were called to Seabreeze Avenue in Newport, South Wales, at 8.40am on Thursday after neighbours reported hearing three gunshots.
They found the pair lying in the road. A gun was later recovered from the scene.
Detectives said the two people involved had previously been in a relationship, which had "come to the attention" of police in the past.
Chief Inspector Huw Nicholas, of Gwent Police, said on Thursday that the force was still trying to establish exactly what happened.
He said: "While I am limited as to what I can say about the people involved, what I can say is it is known that they had previously been in a relationship which had come to the attention of police.
"For this reason we have referred the matter to the IPCC.
Newport is in south Wales "Residents are obviously shocked and distressed ... and we have officers and Community Support Officers in the area who will be available to speak to residents as required."
The couple were taken to the Royal Gwent Hospital in Newport. The woman died, while the man underwent surgery.
It is understood a post-mortem examination on the woman will be carried out on Friday.
The IPCC confirmed it would be examining Gwent Police's previous contact with the man and woman.
Officials say this is standard procedure in incidents such as the shooting.
A spokesman said: "There is a police murder investigation into the shooting of the 46 year-old woman and this will take priority.
"A further statement will be issued by the IPCC early next week."
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