The accord, a treaty covering the life and activity of the Church in Palestine, was the first since the Vatican recognised the Palestinian state in February 2013.
The treaty, which took 15 years of negotiations to complete, was agreed in principle last month and bitterly condemned by Israel as a setback for the peace process.
The Vatican's recognition of the state of Palestine followed a November 12 vote in favour of recognition by the UN General Assembly.
Vatican officials have described it as reflecting the Church's desire to see the conflict in the Holy Land resolved by a "two-state" solution.
The Vatican has had diplomatic relations with Israel since 1993 but has yet to conclude an accord on the Church's rights in the Jewish state which has been under discussion since 1999.
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