All 14 are unaccompanied and will be reunited with their relatives who are already in the UK.
Archbishop Rowan Williams said Britain can expect 150-200 more child asylum seekers in the next few weeks.
The kids have been fast-tracked into the UK as the Home Office step up their plans to reunite families.
But Archbishop Williams criticised the government for the “delay” in bringing children to the UK before the demolition of the camp next week.
French authorities have delayed the demolition of the camp until British government officials workers have identified eligible minors.
There are currently an estimated 10,000 people living in the Calais camps.
New UK legislation, named the Dubbs Amendment, allows under 18s to be reunited with their family.
But proving the age of minors has been difficult as they very rarely have means of identification.
Stephen Hale, chief executive of the charity Refugee Action, said: “It”s fantastic news that, at last, vulnerable children in Calais will be reunited with their families in Britain.
“These children must have the support they need to rebuild their lives when they arrive.”