We consider the direct detection of dark matter (DM) with polar materials, where single production of optical or acoustic phonons gives excellent reach to scattering of sub-MeV DM for both scalar and vector mediators. Using Density Functional Theory (DFT), we calculate the material-specific matrix elements, focusing on GaAs and sapphire, and show that DM scattering in an anisotropic crystal such as sapphire features a strong directional dependence. For example, for a DM candidate with mass 40 keV and relic abundance set by freeze-in, the daily modulation in the interaction rate can be established at 90% C.L. with a gram-year of exposure. Non-thermal dark photon DM in the meV - eV mass range can also be effectively absorbed in polar materials.