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Highlights The p–n segment thermoelectric aerogel fiber was fabricated through an alternating coaxial wet-spinning strategy. Resultant alternating p–n segment thermoelectric fiber was electrically connected in series (two p–n pairs with a length of 3 cm) with an outstanding electrical conductivity of 23.76 S m−1. Thermoelectric textile-based self-powered fire warning electronics exhibited sensitivity (trigger time within 1.43 s) and repeatable temperature sensing performance for firefighting clothing.