The gas phase electronic absorption spectrum of nitrobenzene (C₆H₅NO₂) in the 4.5– 11.2eV region is recorded using synchrotron radiation with a view to comprehend the nature of the excited states. Electronic excited states of nitrobenzene are mainly classified as local excitations with in the benzene ring or nitro group and charge transfer excitations between the benzene and nitro group, with some transitions showing percentage from both. The nature of molecular orbitals, their ordering sand energies are obtained from density functional theory calculations which help in assigning partially assigned/unassigned features in earlier photo electron spectroscopy studies. Optimized geometry of ionic nitrobenzene predicts redistribution of charge density in the benzene ring rather than the nitro group resulting instabilization of the benzene ring π orbitals in comparison to the neutral molecule. Time dependent density functional theory computations are found to describe the experimental spectra well with respect to energies, relative intensities and nature of the observed transitions in terms of valence, Rydberg or charge transfer type. New in sights in to the inter pretation of ¹B_2u→¹A_1g and ¹B_1u→¹A_1g shifted benzene transitions in light of the present computational calculations are presented. The first  few members of then s,np and nd type Rydberg series in nitro benzene, converging to the first six ionization potentials, identified in the spectra as weak but sharp peaks are reported for the first time. In general, transitions to the lowest three unoccupied molecular orbitals 4b₁, 3a₂ and 5b₁ are valence or charge transfer in nature, while excitations to higher orbitals are predominantly Rydberg in nature. This work presents a consolidated experimental study and theoretical interpretation of the electronic absorption spectrum of nitrobenzene.