The Lightning Breathing technique in Demon Slayer is significant because it is a powerful and advanced form of breathing technique used by the Hashira (Pillars) of the Demon Slayer Corps. This technique allows the user to enhance their physical abilities and attack strength by channeling and manipulating electric energy. It is considered one of the most formidable and effective combat techniques in the series, making it a crucial skill for the elite demon slayers in their battle against demons.