Relevant information on PPO crystallization, with particular emphasis on nanoporous crystalline (NC) and related co-crystalline (CC) forms, is reviewed. Preparation methods, structures, properties and possible applications of NC and CC samples are discussed. Reviewed results mainly refer to films (unoriented or with axial or planar orientations) but also to NC powders and NC aerogels. Particular attention is given to the impressive solubility and diffusivity of organic guests, which can be achieved for NC PPO samples. X-ray diffraction patterns and infrared linear dichroism, as collected for axially oriented NC films, indicate the presence of large diameter crystalline helices with intrahelical location of the guest molecules. The final sec...