The very fact that there are windows suggests this isn't the case. If it was that easy to casually transparent-ize the walls, then why bother having windows at all?
This might in fact explain why those windows are at the oddest locations in the outside view - a big concentration in the neck, which is the least habitable part, and noticeable dearth in the saucer rim areas, despite much of the crew supposedly being housed there.
Quite possibly, the windows cover much of the ship, but generally are shuttered by adjusting opaqueness, so that they appear seamlessly
blank from the outside. Additional mechanical shutters may exist on the inside (say, for the portholes of "Mark of Gideon" even if those don't match outside porthole shapes particularly well), but the basic mechanism is one of turning parts of the hull transparent and back with a keypress.