There are tons of crossed signals here, and it started waaaaay back with the title of the thread itself.
"Photoelectric effect", at least the standard one that was modeled by Einstein and tested by Millikan, is done on METALS using visible-to-UV range light source. So the electrons being emitted are from the CONDUCTION BAND of the metal. This is crucial because the energy spectrum of the photoelectrons are continuous, not discrete as in an atomic orbital.
So whenever I read something like this thread, where the OP is asking about inner shell electrons, etc. (i.e. no longer about the bands), then I question on whether this is an x-ray photoemission (XPS) phenomenon where core-level states are now being probed, or if this is a photoionization phenomenon, where the material isn't a solid (metal), but rather a gas. This is NOT your typical, standard Photoelectric effect! There are many aspects of the photoelectric effect model that doesn't quite work in this regime.
In XPS, the low binding energy electrons ARE ejected as well (one can see the Fermi edge in the spectrum), but due to the favorability of the absorption cross-section, the core-level states often dominates in the spectrum. This, in itself, should answer the OPs question, I would think.
I just wish people pay a bit of attention in their use of the terminology. It might eliminate many of the confusing signals and discussion.
Zz.