Development of more sustainable materials for textile-based triboelectric nanogenerators (T-TENGs) is crucial for the on-going transition in manufacturing of next-generation wearable technologies. Sustainability and recyclability of such new materials are important. This facilitates the introduction of cellulose-based materials as an active TENG material. In this work, cellulose acetate, generally recognized as a biodegradable polymer, is used to prepare triboelectric electrospun mats. The electrospinning technique is applied to optimize the cellulose acetate mat morphology, structure, and mechanical properties. The TENG performance and overall mechanical properties are further optimized by combining the electrospun cellulose acetate mats with nylon-6 (i.e., polyamide 6) mats to form the T-TENGs via integration with conductive cotton textile. The mechanical stability and electrical performance of the cellulose acetate and nylon electrospun mats is verified in 50 000 cycles. The formed T-TENG also demonstrated a good triboelectric performance with a maximum peak-to-peak voltage >400 V, maximum current >11 µA, and peak power of ≈3 mW.