Is Shakugan no Shana-tan S hentai?
No
Rated PG-13 (Teens 13 or older) on MyAnimeList and not tagged as Hentai.

Special · 2009 · 4 episodes · PG-13 - Teens 13 or older
Comedy, Parody
Shana-tan specials bundled with the Shakugan no Shana S Blu-ray and DVD. Episodes #1: Shakugan no Shana-tan G #2: Shakugan no Shana-tan 2dos #3: Shakugan no Shana-tan 3tri #4: Shakugan no Shana-tan FRONTIER
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