In recent years, renewable and sustainable triboelectric nanogenerators have attracted attention due to their high energy conversion rate, and enhancing their functionality further contributes to their applicability across various fields. A pH-sensitive triboelectric nanogenerator (pH-TENG) has been prepared by electrostatic spinning technology, with anthocyanin as the pH indicator and environmentally friendly polyvinyl alcohol (PVA) as the substrate. Among many friction-negative materials, the pH-TENG exhibits the best combination with fluorinated ethylene propylene (FEP) and yields an open-circuit voltage of 62 V, a short-circuit current of 370 nA, and a transferred charge of 21.8 nC. At a frequency of 3 Hz, it can charge a 4.7 μF capacitor to 2 V within 45 s, effectively powering a thermometer. Furthermore, the presence of anthocyanin does not affect the pH-TENG's power generation performance and enables the monitoring of a wide range of environmental pH changes, with an ΔE change of 28.8 ± 7.6. Therefore, pH-TENG prepared with environmentally friendly materials can bring new available materials to the biological and medical fields.