A cat experiences the world head first. As such, the head is the center of several important cat communication behaviors, all very different in meaning but more subtle in procedure. Learning the differences in these behaviors will go a long way to helping you help your cat relax and be happy.

Cat Communication: Why Don't Cats Like to be Patted on the Head?
Every cat is different but a cat's instincts tell it to avoid hands reaching for their head. Find out why in this discussion of cat communication.
Head First
Cats Slap Fight
Some cats react so violently to your hand reaching towards their face because that is how a cat fights. Minor altercations usually start with a slap to the side or top of the opposing cat's head. As such, if the cat you are reaching for doesn't understand your intention the cat assumes you mean to do harm and the sheer size of your hand can result in an enhanced fight or flight response.
Mother's Love
A kitten first experiences the importance of the head in the cat world as the mother cat bathes the kitten. The mother cat licks the kitten head to toe but spends a lot of time licking the face and top of the head, much like a human mother might hold and rock a child. This differs from the slap expectation because it is the mother's face approaching the kitten, not the mother's paw.
When socializing a kitten, setting the kitten in your lap and gently using your thumb to stroke the top of the kitten's head can mimic the feelings of the mother cat licking the kitten's head and begin the kitten's journey towards not fearing hands.
Head Thump
People familiar with cats have many names for this behavior. Head butt, head thump, even "owww" is used to describe this particular behavior. Because the paws are used primarily for fighting and killing, cats greet friends by touching the tops of their heads together. When you watch two friendly cats approach you'll notice that just as they meet each other they duck their heads and sometimes turn their heads slightly away before touching skulls. Now, while this may look relatively gentle from a distance, a cat who really likes another cat (or human) they can hit quite hard. I've seen, and experienced, some head butts that seem more like mountain goat attacks than greetings.
Averting the eyes is a big part of this ritual greeting and most cats that are happy with being petting on the head will either turn their heads slightly before you pet them or close their eyes.
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How to Approach a Cat
When you want to pet a tame cat, especially an unfamiliar tame cat, never reach straight at a cat's head from in front of the cat. It is simply too threatening a gesture. Instead, reach from the side for the middle of the back or the scruff of the neck. Move slowly and do not stare as though challenging the cat.
Once the cat accepts petting, you can begin to move towards reaching the skull. After a cat has become comfortable with you they are much more likely to accept and welcome being petted on the head but it takes time for them to learn this behavior.

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