Matrix isolation is an experimental method in chemistry that is widely used for the preparation of samples for spectroscopic studies. It makes it possible to stabilize species which are unstable at room temperature, to isolate molecules in solids from each other, and to carry out molecular spectroscopy at low temperatures. Matrix isolated molecules are studied by a variety of techniques. In this paper the application of inelastic neutron scattering (INS) to matrix isolation is reviewed. Molecules that contain hydrogen atoms are diluted in inert gases such as argon, krypton and nitrogen, and then condensed inside a liquid helium cryostat of the type that is in use at many neutron spectrometers. For this work we developed a technique for the vapor deposition of inert gases with dopants that have low vapor pressure. INS focuses on some aspects of matrix isolation which are not appropriately covered by other spectroscopies, mainly solid state aspects of matrix isolated molecular aggregates and of the matrix itself. Neutron scattering is used to observe optically forbidden excitations such as methyl librations, tunnelling transitions, phonons, and rotational transitions involving a nuclear spin flip. Moreover, a direct correlation of spectroscopic data with the powder diffraction pattern of the matrix is possible with this technique. Localized modes and phonon densities of states can be observed in the same sample and may then be related to the respective diffraction pattern. The vapor deposited samples can be characterized in this way, and possible structural faults in rare-gas lattices revealed which are not usually recognized by other techniques. The structure of molecular aggregates has been elucidated by neutron spectroscopy of their low frequency internal intermolecular modes. HCN forms long linear chains, CH 3CN antiparallel dimers. Both species may, be understood as intermediates for the formation of the respective crystals. The structure of the matrix cages, in which single molecules are embedded, is explored by recording rotational and translational localized modes of these molecules. The single particle rotations of HCl, H 2O, NH 3, and CH 4 were studied directly. Tunnel splittings and librational spectra were recorded from molecules with methyl groups [CH 3CN, CH 3I, CH 3COCH 3, C 3H 8, C 4H 10, Sn(CH 3) 4, and others]. The mutual influence of translational modes of the guest and phonons of the host can be studied, since the neutron spectra are directly connected with the phonon density of states of the system. The librational spectrum of N 2 in Ar and a local mode of H 2 in solid D 2 are presented and compared with theoretical calculations.