The decision comes on the 21st anniversary of the start of the Rwandan genocide in which 800,000 people were killed.
Jean-Pierre Joyet, of the president's office, signed the release of the documents alongside former president François Mitterrand's archivist, Dominique Bertinotti.
A source close to President François Hollande said France must be transparent and help Rwanda in its process of reconciliation.
Ties between France and Rwanda have been strained since Rwandan President Paul Kagame accused Paris of complicity in the genocide because of its support of the Hutu nationalist government that carried out the mass killings, mainly of ethnic Tutsis.
France's Interior Minister Bernard Cazeneuve was one the two rapporteurs in a French parliamentary enquiry into France's role in Rwanda.
He has admitted the French authorities made "serious errors of judgement".
The declassified papers, which include documents from diplomatic and military advisers, will be available to both researchers and victims' groups.