Crystalline modifications, exhibiting largely different X-ray diffraction patterns, have been obtained for poly(2,6-dimethyl-1,4-phenylene)oxide (PPO), by gel desiccation procedures as well as by solvent-induced crystallization of amorphous films. The choice of the solvent allows controlling the nature of the crystalline phase. Both amorphous and semicrystalline samples of this commercial thermoplastic polymer exhibit a high uptake of large guest molecules (like, e.g., benzene or carbon tetrachloride), both from vapor phases and from diluted aqueous solutions. Surprisingly, the semicrystalline PPO samples present guest solubility much higher than fully amorphous PPO samples. These sorption experiments, as well as density measurement...