Accurate mol. and crystal structure and exptl. electron d. distribution in the vanadocene single crystal were established from the precise x-ray diffraction data at 108 K A characteristic asymmetry of the deformation electron d. in the vicinity of the metal atom was found which is attributed to the different occupancies of the 3d-metal orbitals of the V atom. A multipole anal. of the diffraction data was performed and the numerical values of the 3d-metal orbital occupancies in vanadocene were 1st calcd. directly. The results obtained are in agreement with the quantum-chem. calcns. of vanadocene and other 3d-metallocenes.