Spectroscopic probes of the electronic structure of transition metal-containing materials are invaluable to the design of new molecular catalysts and magnetic systems. Herein, we show that 2p3d resonant inelastic X-ray scattering (RIXS) can be used to observe both spin-allowed and (in the V-III case) spin-forbidden d-d excitation energies in molecular vanadium complexes. The spin-allowed d-d excitation energies determined by 2p3d RIXS are in good agreement with available optical data. In V(acac)(3), a previously undetected spin-forbidden singlet state has been observed. The presence of this feature provides a ligand-field independent signature of V-III. It is also shown that d-d excitations may be obtained for porphyrin complexes. This is generally prohibitive using optical approaches due to intense porphyrin pi-to-pi* transitions. In addition, the intensities of charge transfer features in 2p3d RIXS spectroscopy are shown to be a clear indication of metal-ligand covalency. The utility of 2p3d RIXS for future studies of complex inorganic systems is highlighted.