<p>The good optical quality of non-linear optical semi-organic single crystal CA5SS -VO²⁺ was formed from sequential re-crystallization processes by slow evaporation from solution growth technique at room temperature measurement. Electron Paramagnetic Resonance experiments on the grown single crystal were carried out using the most sensitive EPR spectroscopy with an X-band microwave frequency as an input signal at room temperature. The angular variation of the EPR hyperfine line spectra across multiple crystallographic planes revealed two magnetically comparable VO²⁺ sites in the CA5SS single crystal system. The computed spectroscopic splitting factor ‘g’ and hyperfine splitting factor ‘A’ show that site I(g_xx=1.996;g_yy=1.973;g_zz=1.927,A_xx=61;A_xx=105;A_xx=178) is in rhombic and site II (g_xx=1.998;g_yy=1.993;g_zz=1.932,A_xx=59;A_xx=81;A_xx=192) is in axial field symmetry around the impurity ion VO²⁺ of the crystal system. Site I and site II paramagnetic impurity ions take the place of a monovalent (Ca⁺) cation and S(1) in the host lattice’s substituitonal space. The molecular orbital coefficient values were used to compute the impurity ion’s covalent bonding with the host lattice. The impurity ion’s ground state wave function is calculated from the Rache parameter (R_I =1.106, R_II =1.204), using the spin Hamiltonian parameter.</p>