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Top Notch is an item currently existing as only a single copy, owned by Notch (of course).
Are there any other limited or unique items in either TF2? ("Limited" meaning items which were only ever available in a fixed quantity, i.e. there was never a time when they were freely available.)
The J.Axer's Dapper Topper, Amber's Rad as All Hell Hat and Uncle Sam are unique. There is only one of each, and they were awarded to the first, second and third place winners in the Propaganda Contest.
Some items were gifted in Self-Made quality to their creators. Where an item was credited to a single creator, the Self-Made version of that is the only one in that quality, although this isn't as truly unique as the item is more widely available in normal quality.
Other than the Top Notch, these are the only one-of-a-kind items in TF2.
Other rare items (fewer than 1,000 awarded) include:
I guess it somewhat depends on how "unique" an item has to be. For instance, there are certain versions of weapons that are given to key community members, or to the person who actually created the item. Valve employees also have a special class of weapon that is reserved for them. There's a page on the TF2Wiki that describes these and links to some lists.
There's also the weapons made of Australium, including the Golden Wrench and the Saxxy, of which there are very, very few.
This website (As of 2019, this site has gone down. You may be able to find another website that has information on backpack item frequency.) scans backpacks and keeps stats of items. If you choose a category, not only can you see the relative popularity of items, but if you scroll all the way to the bottom you can see some rare items are owned by less than 0.01% of the players in their database.
In addition to Jonathan Drain's list, some more interesting items:
