Number 1
In From Russia with Love, SPECTRE's chief appears only as Number 1: a faceless man shot from behind, stroking a white cat. When chess master Kronsteen's plan fails, he has him executed on the spot with the poisoned blade in a henchman's shoe and gives Rosa Klebb one last chance.
In Thunderball he chairs a SPECTRE meeting in Paris, hidden behind a refugee aid organization, and electrocutes a member in his chair for skimming money. The atomic bomb plot goes to Emilio Largo, Number 2. His face stays hidden.