We report a detailed investigation of structural, electronic, and spectroscopic properties of VSc 2 N@C 68 endohedral fullerene. First, the candidate structures of the ground state are obtained using a systematic approach in which 900 isomers of endohedral fullerenes were screened for their energetic stability. The stability of some of the most promising isomers was studied using density functional theory at the all-electron level using large polarized Gaussian basis sets. Although the dopant vanadium atom is also in the same charge state as Sc, the doping changes the structure and the spin state from that of Sc 3 N@C 68 . The d-orbitals of the V atom lead to a spin state with spin moment of 2 μ B for the endohedral fullerene. The spin− orbit coupling strength is, however, weak, leading to vanishingly small zero-field splitting of the spin levels. The ionization energy, electron affinity, and the quasi-particle gap of the most stable isomer are comparable to those of C 60 . The vibrational frequency analysis shows that the structure is stable. Finally, the infrared, Raman, and optical spectra of the most stable fullerene are calculated, which can aid in identification of the cluster in experiments.