Officers launched a murder investigation after finding the woman dead at the scene inside De La Mer House on Naze Park Road shortly after 9am.
Local reports say the woman was shot and detectives say a revolver has been recovered and a man - believed to be her husband - was arrested at the scene on suspicion of murder and remains in police custody.
Essex Police said the man was also a resident at the home.
Detectives from the Kent and Essex Serious Crime Directorate have taken over the investigation.
Detective Chief Inspector Simon Werrett, from Essex police, said: "At this stage we are not looking for anyone else in connection with the investigation and our enquiries are ongoing."
Douglas Carswell, the UKIP MP for the area, said he was "very shocked" by the news.
"It's very shocking. If you have got a loved one in a care home, you expect them to be safe," he said.
"People need to know the exact circumstances of what happened, it is extremely disturbing. Walton-on-the-Naze is supposed to be one of the most peaceful and tranquil places there is - elderly people want to be in a peaceful and tranquil environment.
"Of all the places you expect this to happen, this is the last. I know the care home well, I have been several times. I know the staff are very good people and they must be fairly shocked by this."
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