X-ray photoelectron spectroscopy is used to probe the photoinduced shifts in the binding energies of Si2p, O1s, and C1s of the SiO2/Si interfaces of a number of samples having oxide and/or thin organic layers on top of p- and n-Si wafers. Whereas the photoinduced shifts, in each and every peak related, vary from 0.2 to 0.5 eV for the p-type samples, the corresponding shifts are substantially smaller (<0.1 eV) for the n-type, regardless of (i) oxidation route (thermal or anodic), (ii) thickness of oxide layer, (iii) nature of organic layer, or (iv) color of three illuminating sources we have used. This leads us to conclude that these particular photoshifts reflect the charge state of the SiO2/Si interface, even in the case of a 20 nm thick oxide, where the interface is buried and cannot be probed directly by XPS.