Candidates for the PNC are nominated by a committee consisting of the PLO Executive Committee, the PNC chairman, and the commander in chief of the Palestine Liberation Army. After nomination, PNC candidates are elected by a majority of the entire PNC membership. However, due to the impossibility of holding elections, PNC elections have never been held and most members are appointed by the Executive Committee.
In 1996, when the Council had to vote on the revision of the Palestinian National Charter, the total number of PNC members was increased with 400 to about 800. By 2009, some 700 from them had remained. As of 2003, the PNC chairman was Salim Zanoun and the PNC had 669 members; 88 are from the first Palestinian Legislative Council (PLC), 98 represent the Palestinian population living in the West Bank and Gaza Strip, and 483 represent the Palestinian diaspora. While the PNC has a number of PLC members, it is not an organ of the Palestinian Authority. Rather it is the equivalent of PA's PLC.
The first PNC, composed of 422 representatives, met in Jerusalem in May 1964 and adopted the Palestinian National Covenant (also called Palestinian National Charter). It also established the PLO as the political expression of the Palestinian people and elected Ahmad Al-Shuqeiry as the first chairman of the PLO Executive Committee. At the conference were representatives from Palestinian communities in Jordan, West Bank, the Gaza strip, Syria, Lebanon, Kuwait, Iraq, Egypt, Qatar, Libya, and Algeria.