This shouldn't be happening, and though you can fix it by manually urldecode()ing, you will probably be hiding a basic bug elsewhere that might come round to bite you later.
Although when you POST a form using the default content-type ‘application/x-www-form-encoded’, the values inside it are URL-encoded (%xx), PHP undoes that for you when it makes values available in the $_POST[] array.
If you are still getting unwanted %xx sequences afterwards, there must be another layer of manual URL-encoding going on that shouldn't be there. You need to find where that is. If it's a hidden field, maybe the page that generates it is accidentally encoding it using urlencode() instead of htmlspecialchars(), or something? Putting some example code online might help us find out.