Alan, Yes it will work, but the problem with CA glues (cyanoacrylate) is you have very little time to work. If your piece is not positioned properly before the glue sets, your are out of luck! So you want a glue that allows a little wiggle room.
I think Titebond sells a crown molding glue that will do what you want. It grabs real fast, but allows time to adjust your work.