Organic molecules have been discovered, which can be utilized as synthetically prefabricated molecular pore templates for the construction of self-assembled porous molecular materials. They have shown permanent porosity to gas molecules or selective guest binding in either crystalline or amorphous solid state. The porosity of these materials is a result of both of the intrinsic molecular voids and extrinsic voids from the inefficient packing. Moreover, the packing motifs can be directed by the functionality of molecules, giving control over the pore connectivity. Pore molecular solids are of interest for a wide range of applications in gas storage, separation, and molecular recognition. Herein, we describe a series of porous organic molecules in terms of both synthetic and computational approaches. Molecular simulations offer a unique perspective by allowing the examination of the structures on the molecular level, and also give additional insight into understanding the nature of these materials and assist in the design and tailoring for specific applications.