The Westcountry Ambulance Trust has taken delivery of 400 chemical suits and extra decontamination showers at a cost of £700,000.
The allocation is the largest of any ambulance service in England
Ambulance services across England have received £5m of protective gear.
The number of chemical suits bought in the Westcountry is the largest of any ambulance service.
The suits and showers will be used by staff dealing with chemical spills on roads and in factories.
But they could also be used after a terrorist act involving chemical or biological agents.
There is no increased intelligence to suggest that the Westcountry is at risk
Neil Le Chevalier, emergency planning officer for the ambulance trust said: "Two years ago the NHS did a survey of ambulance services and A&E departments to find out how ready they were for chemical incidents.
"They found that we were ill-prepared and hence we have the suits today."
He said that since the terrorist attacks on New York in 2001, ministers had said the suits should be able to protect people from chemical and biological attacks.
Mr Chevalier added: "There is no increased intelligence to suggest that the Westcountry is at risk."
A team of 20 paramedics would be fully trained in the Westcountry's main cities, and would able to respond to incidents 24 hours a day.
Earlier this week it was revealed the government is planning to publish a booklet of precautions against chemical and biological attacks.