The selection mechanism in the Discrimination Induced by Variable Angle Minipulse (DIVAM) sequence as a domain filter is investigated using spin dynamics simulations. Experiments on poly(vinylidinefluoride) (PVDF) show that 19F DIVAM selects on the basis of relaxation and the chemical shielding anisotropy interaction, where the role of the latter was confirmed by the simulations. The DIVAM filter was applied in domain selective 13C{1H,19F} experiments on poly[bis(trifluoroethoxy)-phosphazene] (PBFP). The resulting spectra were sensitive to morphological changes in the crystalline domain, which was not previously observed with 19F and 31P methods.