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I counted only 21 instances where Miyuki says "Onii-sama". This was clearly not enough.

Mahouka Koukou no Rettousei Movie: Hoshi wo Yobu Shoujo Characters

The following is a full list of characters and their Japanese voice actors for the anime Mahouka Koukou no Rettousei Movie: Hoshi wo Yobu Shoujo

Tatsuya Shiba

Yuuichi Nakamura

Miyuki Shiba

Erika Chiba

Angelina Kudou Shields

Mayumi Saegusa

Leonhart Saijou

Takuma Terashima

Kokoa

Mizuki Shibata

Katsuto Juumonji

Shizuku Kitayama