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Obviously, Kid Naruto. Actually, a point could be made there considering he was S-Class when using the Kyuubi, he beat Shukaku after all (albeit outside of Shukaku's advantage and with Gaara as a weak spot) and can spam the hell out of shadow clones combined with Regenerationn hax.
Realistically though, the earliest character that I could picture beating Piccolo would be either Kakashi, Hiruzen, Orochimaru or Jiraiya. I think we can dismiss Kakashi since he was actually a lot weaker (according to in-story dialogue). Hiruzen, Orochimaru and Jiraiya are all superior to Part 1 Naruto though (especially with Orochimaru fighting 4-tails Naruto and base(?) Jiraiya sealing 4-tails Naruto).