We have started using it for roof sheathing on jobsites. Our climate is hot so most of our effort is spent in repelling heat. It makes a noticeable difference in attic temps. I haven't measured with a thermometer to compare, but worked in a split attic where an addition had it & the existing house didn't. My sweat meter indicated that the foil section was much cooler.
When we re-roofed our shop a few years ago we used it. It is much cooler in the summer & I don't think we fire up the heaters nearly as often in the winter. It seems like it would have to be effective to some degree for walls (no pun intended), but I have no real knowledge as to how much. My guess is that it would probably help, but it would be pretty disappointing to line walls with to find out that it is really only effective at the heat levels generated by a sun soaked roof.
The glare off it can be pretty overwhelming. Like a 4x8 mirror. We have to be careful to not blind anyone while loading it on a sunny day. And you can sure feel the reflected heat off of it if you turn it towards the sun. As stated above the foil normally faces the air space, so on a roof it faces down. For walls I would think it would face the studs. If it faced the room uncovered the glare could be an issue. I don't know how it is in regards to its fire rating.