From TF2 Wiki
Miscellaneous items (usually abbreviated as Misc. items) are wearable items with their own 'Misc' section in the loadout screen, though they count as headgear for crafting purposes. In a similar fashion to hats, they have no effect on gameplay and exist for cosmetic purposes only (with the exception of polycount set hats). As they occupy their own equipment slot(s), they can be worn in conjunction with many hats. Misc. items are either unlocked through acheiving certain requirements, or dropped during in-game playtime.
There are currently 10 class specific miscellaneous items, and 13 others for use by all classes.
History of Miscellaneous Items
The first misc. item, the Soldier's Gentle manne's service medal, is added to the game. The medal is awarded to the first 11,111 users who stumbled upon a hidden page on the Team Fortress blog, with each medal featuring a unique number. The medal can now only be obtained via trade and will usually fetch a hefty amount.
The Camera beard hat for the Spy becomes a misc. item, allowing it to be worn with other hats for the class. This increases its drop rate to that of normal weapons, resulting in a loss of its rare value and a significant increase in the amount of players that own it. The beard may be 'painted' as to add more rarity or adding better looks.
The first set of community hats from Valve's Contribute! site are patched in, along with a new misc. item for the Medic, the Physician's Procedure Mask. The Camera beard's drop rate is restored to the same drop rate as normal hats. Misc. items can now be used along with hats in the Rebuild Headgear recipe.
The 119th Update
The Primeval warrior medal is awarded to all players who participated in the original beta release of Team Fortress 2, with the medals of those eligible being changed accordingly.
The Whiskered gentleman hat for the Pyro was reassigned to the Misc. slot, so that it may be worn with other hats.
The Mac Update
The Earbuds are added in. The Earbuds are awarded to players who launch TF2 on a Mac between June 10, 2010 and June 14, 2010.
The Dueling medals are awarded to players depending how many duels they have won, the more, the better the medal.
You can also get a companion cube (from Portal) pin.
From Poker Night at the Inventory, you can win License to Maim for every class and Dangeresque, Too? for the Demoman.
This update added the Blighted Beak for the Medic. This item was originally a hat, but due to the community sending e-mails into valve it was later changed in to a misc. item in the next update after Christmas.
Purchasing Monday Night Combat between January 24, 2011 and February 1, 2011 awarded players The essential accessories, Athletic supporter, and The Superfan.
Slogans for the medals, in the 119th Update
Primeval warrior: "A true warriors medal, given to those who fought before the battle even started"
Grizzled veteran: "Display this on your chest proudly, soldier. Each time you kill someone, they'll know they weren't the first"
Soldier of fortune: "Sure some have been doing it longer. But you've proven few can do it better"
Mercenary: "Even though you were late to the party, you were still the life of it."
List of Miscellaneous Items
Because of the special nature of most Misc. items, they are generally incompatible with the crafting system. Most of them cannot be crafted into other items, or crafted themselves from other items. The exceptions are Misc. items that can be found in-game through the item drop system. These items are treated exactly the same as hats. Meaning they can be crafted using any blueprints that may create a hat, or used in place of a hat in blueprints that require a hat. These are the current Misc. items that function as hats, in order of their addition to the game:
These items are considered hats, but they are placed in the miscellaneous slot because they don't take up space on top of the head. This is to allow players with these items to wear them at the same time as a traditional hat. This also allows players to be able to wear two unusual particle effects at once. Both the Le Party Phantom and the Blighted Beak can be unboxed with unusual particle effects.
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