A better resolution of ESR spectrum of bis(2-hydroxyl-phenylketoxime)copper (Ⅱ) complex intetrahydrofuran (THF) solution, measured at liquid nitrogen temperature, was analyzed. From thespectrum, we have not only got hyperfine splitting of the ~(63)Cu and ~(65)Cu, but also very nice super-hyperfine splitting arising from ~(14)N nucleus. The g_x, g_y, g_z; A_x~(63), A_y~(63), A_z~(63); A_x~(65), A_y~(65), A_z~(65); A_∥~N andA_⊥~N etc. tensor parameters were determined rather reasonably. From these, we calculated the bondingparameters of this complex, and discussed its electronic structure. A better resolution of ESR spectrum of bis (2-hydroxyl-phenylketoxime) copper (II) complex intetrahydrofuran (THF) solution, measured at liquid nitrogen temperature, was analyzed. From the spectrum, we have not only got hyperfine splitting of ~ ) Cu and ~ (65) Cu, but also very nice super-hyperfine splitting arising from ~ (14) N nucleus. The g_x, g_y, g_z; A_x ~ 63, A_y ~ 63, A_z ~ ; A_x ~ (65), A_y ~ (65), A_z ~ (65); A_∥ ~ N and A_⊥ ~ N etc. tensor parameters were determined rather reasonably. From these, we calculated the bonding parameters of this complex, and discussed its electronic structure.