In this letter, we report on Work Function (WF) measurements performed at deca-nanometer scale on various metals using Kelvin probe Force Microscope (KFM). We first demonstrated the relationship between the WF value and the grain crystallographic orientation by combining KFM and Electron Back Scattered Diffraction (EBSD) performed over the same Cu area. Once this relationship was established, KFM was used to provide, in addition to WF value, crystallographic properties of TiN PVD films grown on various substrates. Finally we characterized the effect of N2/H2 plasma treatment on the WF of TiN grown by CVD. In the latter case, the modification of the bulk chemical potential by post-treatment was proposed.