The crystal structure of the inclusion complex of phenol in the matrix formed by the trans isomer of meta, meta'-bis-diisopropoxyphosphoryldibenzo-18-crown-6 was determined by X-ray diffraction methods. The molecular structure of the crown ether and the packing of the molecules in crystal is discussed. The statistical disorder of the phenol molecule in two positions with occupancy of 0.5 is due to the location of the molecule on the crystallographic two-fold axis. Additionally, the disorder of the phosphoryl substituent was revealed. Interaction between the hydroxyl group, as well as the hydrogen atom in the ortho position of the phenol with the system of oxygen atoms of the crown ether in the crystal influences the conformation of the macrocycle. In solution the host and guest molecules are associated by the hydrogen bonds formed between the hydroxyl group of phenol and the oxygen atom of the exocylic phosphoryl group of the crown ether.