What is the pathway of the Guis's materials and images? I have search it everywhere in the pk4's.

you set it on the model's spawnflags in the level editor. I recall that there is a chooser once you try to edit that particular spawnflag, so you can preview which gui you're selecting for the model. I may be mistaken, as I haven't edited in a while.
I don't mean the path from the doom 3 editor.I mean the path to the ".mtr" and "tga's" in the pk4 archive.I need to read the mtr file to understand how to use GUIS materials.

use winzip to extract your pk4 files. it's a standard zip archive with a pk4 extension.
The only way to determine what images are used is to examine the GUI markup itself. Sometimes they reference images directly. Other times they reference material shaders.
What is the pathway of the Guis's materials and images? I have search it everywhere in the pk4's.

you set it on the model's spawnflags in the level editor. I recall that there is a chooser once you try to edit that particular spawnflag, so you can preview which gui you're selecting for the model. I may be mistaken, as I haven't edited in a while.
I don't mean the path from the doom 3 editor.I mean the path to the ".mtr" and "tga's" in the pk4 archive.I need to read the mtr file to understand how to use GUIS materials.

use winzip to extract your pk4 files. it's a standard zip archive with a pk4 extension.
The only way to determine what images are used is to examine the GUI markup itself. Sometimes they reference images directly. Other times they reference material shaders.