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The main article can be found at Minecraft Wiki: Mob head.
Mob Heads are decorative blocks. There are five variants of mob heads: Skeleton, Wither Skeleton, Zombie, Creeper and Player. The Wither Skeleton variant is a rare drop from the respective mob, with the other heads available using the Vorpal enchantment. If CoFH Core is installed, it can be configured to make all mobs that have heads drop them with a 5% chance when killed by the player.
The main use of heads is as decoration. They can be oriented in 16 different directions on top of a block, and 4 directions on the sides of blocks, similar to signs. They cannot be placed on top of each other.
Heads are also used in the crafting of Firework Stars. Firework Rockets crafted with said stars will have a creeper shaped explosion, regardless of which type of head was used.
The player can also wear heads as disguise, similarly to pumpkins. This will only replace the first layer of the player's skin. If the player has a second layer over their head, it will still render over the head. Occasionally, another mob may pick up a skull and wear it just as the player would. This is common when a wither skeleton drops a skull next to another mob in the nether. They can also be used as a decorative disguise, using dyed leather armor. Heads are not able to be pushed by pistons, as they have tile entities.