A pi-d hybrid electronic system, (DMe-DCNQI)(2)Cu, where the pi orbital of the organic molecule, DMe-DCNQI, is strongly hybridized with the d(xy) orbital of Cu, has been studied by N-15 and C-13 NMR at three sites. The analysis of Knight shift, K, local Spill susceptibilities in the pi and d orbitals were determined separately. The pi and d spin susceptibilities were found to be quite different in magnitude and temperature dependence. Moreover, the Knight shift was separated into those of two constituent bands; a one-dimensional pi band and a three-dimensional pi-d band. The relative weight of the band susceptibilities is strongly temperature-dependent.