Madara, nicknamed "Nyanko-sensei," runs into two young children when he gets separated from his temporary owner Takashi Natsume. Unequipped to handle kids, Nyanko-sensei tries to wriggle his way out; but fearing for their safety around the ravenous forest youkai, he decides to escort the siblings to safety. However, even for an all-powerful youkai such as Nyanko-sensei, dealing with the playful and overly curious nature of children can prove to be an exhausting challenge.

Natsume Yuujinchou: Nyanko-sensei to Hajimete no Otsukai was bundled with the Blu-ray and DVD release of Natsume Yuujinchou: Itsuka Yuki no Hi ni in Japan on February 5, 2014. It was originally included in a DVD special available in the August 2013 issue of LaLa to commemorate the manga's 10th anniversary.

The special was later broadcasted on November 16, 2016 due to certain circumstances regarding the broadcast of episode seven of Natsume Yuujinchou Go.