That would be lost in history. Karate can be documented back in to the early 1800's and Martial Arts back many centuries. The various arts were blended and became karate on Okinawa in the late 1800's. Matsamora is considered by many to be the first known instructor.
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It is difficult to tell. Karate was developed over a large time period and by many masters developing their own styles. Karate is like an umbrella that covers all those styles. But I know that Itosu AnkÅ is considered a legenday master who taught people like Funakoshi Gichin and Kenwa Mabuni.