It's NOT wrong. It's just not common usage and it means something different from what you probably intend. We normally say we are "on the way home".
The word "home" is flexible. It can be a noun, an adjective, or an adverb. Here are examples:
NOUN: "I live in a home"
ADJECTIVE: "This is my home address"
ADVERB: "Let's go home", "I'm on my way home"
The sentence "I am on the home way" is perfectly grammatical, but let's think about what it might mean. I would interpret "home" as an adjective modifying the noun "way". I would interpret "way" as synonym for "road". Thus, I would interpret "I am on the home way" to mean that I am on the specific road that leads to my house.
That is quite different from the meaning of "I am on the way home". As long as I am driving towards home, I am on my way home, regardless what road I am on. However, I am only on the "home way" when I am on the specific road that goes to my house.