In the present paper we report the results of a multiconfigurational computational study on potentialenergy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S2(ππ*) and S1(nπ*) states. We have found that there is a singlet state, S3 at the trans geometry, on the basis of the doubly excited configuration n2π*2, that has a deep minimum at about 90°of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S2(ππ*) and for the wavelength-dependence of azobenzene photochemistry. We have characterized the S1(nπ*) state by calculating its vibrational frequencies, which are found to correspond to the recently observed transient Raman spectrum. We have also computed the potential-energy curve for the triplet T1(nπ*) at the density functional theory B3LYP level, which indicates that in this state the isomerization occurs along the twisting coordinate.