The valence electron structure and magnetic properties of Nd2Fe14B intermetallics have been investigated using empirical electronic theory of solids and molecules. The calculations fit the experimental data well. It reveals that the magnetic properties of Nd2Fe14B are proportion to the 3d electrons of Fe atoms. The moments increase from the Fe at 4c site to the Fe at 16k2 site, which is due to the changes between the valence electrons, dumb pair electrons and 3d magnetic electrons. According to the calculation, 78% of dumb pair electrons and 18% of valence electrons in d orbit change to magnetic electrons, this causes the increase of moments from the Fe at 4c site to the Fe at 16k2 site. Both Curie temperature and moments are proportion to the coordination numbers of the Fe atom, however, the Curie temperature decrease with the weighted equal bond numbers Iσ. The effect on Curie temperature of non-magnetic elements Nd and B is derived from the change of the Fe—B and Fe—Nd bond distances.