I know what most people think of "Best Of", but you absolutely cannot go wrong with this recording.
First, the overture of the Barber of Seville is probably one of the most authoritative - I own four different versions of that opera and they all pale by comparison. It's similar of Largo al factotum, Figaro's aria - Gobbi is simply stellar.
It also contains very interesting pieces like the Cat's Duet, parts of William Tell which is really hard to find given the cast and setup it requires, and overall a wonderful selection.
The recording quality is very good, although it sets the listener a little far from the scene as opposed to being in the front row, but does not make it less enjoyable.
Fits any collection, large and small. A true must have for Rossini enthusiasts.