As with any other type of release location, there's no hard and fast Yes or No.
Some hotels like them, some don't. I've had staff chase me down to say, "You left your book behind." (To which I ususally say, "No, it's not mine," since once I release it, it is no longer mine.)
But in a neighboring town there is a hotel with a big bookcase and they are fine with me releasing there. As a matter of fact, I found out that at one time a former manager had a staff member register a bunch of books for the shelves. I don't think they still actively do that, but they don't have any problem with me leaving mine there.
Then again, some hotels may put them in lost and found, or even throw they out. If I was going to release one or two, I might take a chance, but if I hoped to release a bunch I'd probably ask to make sure it was okay with the hotel.
But this is true for any type of establishment. One pizza shop staffer told me the manager said any books left there would be thrown out. Another pizza place let me bring in a large bookcase for a OBCZ (Official BookCrossing Zone).
ETA: I just added a picture of that bookcase to a book I released there recently. Click on the image in the release note to enlarge it. http://www.bookcrossing.com/---/14427748
Some Starbucks don't want books; I have one in my area that is okay with a small amount of books being released there, so I might leave half a dozen. It just varies. And by asking, you can be sure your books aren't in a place where they'll be tossed, and also spread the word about BookCrossing.
And sometimes things change. The release spot where I and my BookCrossing friends left the most books over the years is here: http://www.bookcrossing.com/---/64347
. (You'll have to click View All on the Go Hunting page to see the books, I believe.) We've been releasing there since 2003 according to the oldest dates and it looks like there were 5,346 books released there over the years that were never "caught." That doesn't mean they are still there, they've all been picked up, but those are the ones that haven't yet been journaled. And yet, after 14 years and over 5,000 books, all of a sudden a few months ago it "was against corporate policy" and we can no longer release there. The customers and staff loved the books and were disappointed, but the bosses didn't want them. So you never know.
The same changes can occur at restaurants. At one time a local Ruby Tuesday said No. Now, with a different manager, it's okay to leave books.
ETA: I just noticed you also asked where inside the hotel to leave the book so they will get caught quickly. Again, in my opinion, that is completely up to chance. No location can guarantee you a catch. And even places where all the books are picked up don't guarantee a journal entry, as you can see from the link to Denny's above. Of course, we did get many catches from there, but there are a lot of books that were picked up and never journaled. Though I never give up. According to the Site Watch forum a book was just journaled 14 years after it was released, so there's always hope!