Electron paramagnetic resonance (EPR) and optical absorption studies of vanadyl ions in lithium hydrogen oxalate monohydrate single crystal and powder are reported at room temperature. Single crystal rotations in each of the three mutually orthogonal crystalline planes, a b ∗ , b ∗ c ∗ and a c ∗ indicate four different vanadyl complexes. The detailed investigation of EPR spectra indicates that one of the VO 2 + sites (the intense one) may enter the lattice substitutionally and the other three occupy the interstitial positions. From the angular variation, the spin Hamiltonian parameters are evaluated and discussed. The optical absorption spectrum shows four bands. From the optical and EPR data, various bonding parameters are determined and the nature of bonding in the crystal is discussed.