Several approaches may be used to link the Raman spectra to the characteristic size scale of nanomaterials. To treat the vibrations of the nanocrystal as localized phonons is a basic idea of the phonon confinement model (PCM). This review describes different approximations proposed since the pioneering work of Richter et al. in 1981. Early implementations of PCM received criticism for the arbitrariness of the introduced parameters and physically unsound assumptions. Later, the physical consistent version was proposed in which the model was coupled with quantum‐chemical calculations. Representative cases of applying the PCM are discussed: model benchmark system (nanodiamond), localized acoustic phonons in nanoparticles (ZnO), nanowires (Ge), and phonon‐like modes in the hydrogen‐bonding network of liquid water.