From absorption spectra and PL data you can easily find HOMO-LUMO gap of the material. Then Valence band spectra of XPS will help you to find out exact position of Valence band(HOMO) from the Fermi energy(Ef). VB energy and band gap will help you to find exact position of CB(LUMO).
This question has already been discussed here and have a look at the answer there. It was answered by Dirk Luetzenkirchen-Hecht and he rightly pointed out to a very relevant paper which might also help you finding the answer.