This study confirms the existence of several nanometer-ordered structures in amorphous Al2O3–2SiO2–Na2O–7H2O geopolymers by high-resolution transmission electron microscopy and selected area electron diffraction. The composition ratio of the geopolymers was designed according to the NaA zeolite composition (Si/Al/Na atom ratio of 1:1:1), and the expected NaA molecular sieve was achieved by the Al2O3–2SiO2–Na2O–7H2O geopolymers through a hydrothermal reaction. This design concept was used to convert geopolymers into zeolite molecular sieves and provides a new preparation method for zeolite membranes or zeolite bulk materials.