The 21-strong team was put together within 24 hours of the initial request by Home Secretary Priti Patel, who visited Greece this week.
The team will be led by officers from Merseyside Fire & Rescue Service (MFRS), the lead authority for National Resilience, and overseen by MFRS’ deputy chief fire officer Nick Searle in his lead role for National Resilience.
Other firefighters are from Lancashire, London, South Wales, West Midlands and the NRAT (National Resilience Assurance Team).
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The fires have obliterated vast swathes of forest and burned scores of homes in Greece with more than 1,000 people having to be rescued by sea as flames engulfed the island of Evia.
One volunteer firefighter has been killed in the fires, which have been raging for days.
MFRS’ chief fire officer Phil Garrigan said: “Our Greece counterparts are struggling to deal with the scale of the wildfires. These fires are devastating the communities and putting lives at risk and it is only right that we as a country assist.
“The team of 21 firefighters will offer professional and technical skills to our friends and colleagues in Greece at a time when they need us most.
“I have no doubt that our teams will do all they can to assist our colleagues in Greece, along with their communities, during these devastating wildfires.
“I am extremely proud that we and other Fire & Rescue Services from across the country have been able to step up and mobilise a team within 24 hours of the initial request.
“It is by no means a surprise – helping people is what we do and our desire to help will not be limited by borders.”
The deployment comes following a formal request to the National Fire Chiefs Council’s (NFCC) National Resilience team from the Home Secretary to give operational assistance to Greece.
The Home Secretary said: “I’ve seen first-hand this week the devastating wildfires ripping through Greece and the UK stands shoulder to shoulder with our Greek friends at this difficult time.
“I am immensely grateful to the brave firefighters for stepping forward and volunteering to help and their expertise will be invaluable in supporting the Greek emergency services.”
Greece is suffering its most severe heatwave in 30 years, with temperatures soaring to more than 40C in some areas and more fires likely with forecasts of strong winds and searing temperatures.
Greek and European officials have blamed climate change for the large number of fires that burned through southern Europe in recent days, from Italy to the Balkans, Greece and Turkey.