Photoexcitation spectra of benzene in rare gas matrices show a previously unreported transition near 46000 cm -1. The observed bands are not explicable in terms of site splittings, impurity states, aggregation effects, intermediate radius states of the matrix, triplet states, excimer states, exciplex states or σ-π ∗ transitions. The vibronic spacings in these spectra could be those expected for a 1E 2g ← 1A 1g transition and on this and other evidence we argue that the ordering of origins of the first four spin allowed intravalence states of benzene is 1B 2u (38086 cm -1), 1E 2g (near 46400 cm -1), 1B 1u (48450 cm -1) and 1E 1u (55430 cm -1). Our data also show that the transition 1B 1u ← 1A 1g accounts for most of the intensity of the 210 nm absorption band system. Our ordering of the spin allowed states permits interpretation of experimental data of others, confirms certain semi-empirical and ab initio SCF MO CI calculations in which account is taken of higher excitations and illustrates the necessity of including such higher excitations. The intensity of the 1E 2g ← 1A 1g transition is at least an order of magnitude less than previously calculated indicative of the difficulty of choosing suitable wavefunctions for the 1E 2g state and of calculating "forbidden" transition probabilities.