No.
Ask/request when you make the reservation, and specify what you want (high floor, view, suite, etc.)
At check-in, ask again.
Experiences vary, depending on hotel capacity (special events, high rollers in town) attentiveness of check-in person, etc. That's the meaning of "Upon availability".
Mostly, the first room that comes up on the computer as clean and ready is what you get, unless you ask.
