We report here the synthesis, crystal structure and Electron Paramagnetic Resonance (EPR) studies of the compound bis[1,3-di(p-n-octylphenyl)propane-1,3-dionato]oxovanadium(IV) abbreviated as C-8(VO)C-8. The molecular crystalline properties of this compound are dealt with in this paper. The compound crystallizes in the triclinic, P1 space group with a = 11.956(4), b = 15.802(5), c = 16.293(4) Angstrom, alpha = 103.22(2), beta = 110.61(2), and gamma = 90.88(3): Z=2. The two vanadium centers are crystallographically equivalent and the shortest V-V bond distance is 9.5803 Angstrom. The hyperfine splitting pattern in single crystal EPR spectrum clearly shows the presence of weak pair-wise magnetic interaction. The splitting originates in a combination of hyperfine and One structure caused by dipolar and exchange coupling of nearest-neighboring molecules related by inversion through the unit cell origin. The sign and the value of the exchange coupling constant, J = + 30 G, was determined by simulation of EPR spectra. The principal g and A values obtained are g(\) = 1.934 and g(perpendicular to) = 1.982, A(\) = 192 G and A(perpendicular to) = 69 G.