Phosphoryl fluoride was characterized by Raman spectroscopy and X-ray diffraction analysis. The X-ray structure was obtained by in-situ crystallization. Phosphoryl fluoride crystallizes in the trigonal space group Pm1 with two formula units in the unit cell. In the crystal structure zigzag chains are observed which are formed by intermolecular P–O contacts. The Raman spectra of neat and matrix isolated POF3 display an extra line, which indicates intermolecular interaction in the solid state. Therefore quantum chemically calculation of a POF3 oligomer was performed. The theoretical calculation indicates that the extra Raman line is caused by side splitting of the P–O valence vibration.