Designing a high-performing triboelectric novel material with eco-friendly, rapid, and cost-effective synthesis is the future of material research in triboelectric nanogenerators (TENG). We report a mechanochemical ball mill synthesis of a zeolitic tetrazolate framework (ZTF-8) that is isostructural with the well-known zeolitic imidazolate framework ZIF-8. ZTF-8 is extremely stable in water, 0.1 M aqueous acid/base solutions for 75 days at 25 °C, and boiling water (100 °C) for 7 days. Kelvin probe force microscopy and molecular electrostatic surface potential computational analysis exhibited that ZTF-8 has a very high positive surface potential. Atomic force microscopy and three-dimensional digital microscopy studies reveal the high roughness profile in the ZTF-8 film. The unique structure, exceptional acid/base stability, good dielectric property, and high roughness profile combined with the extremely electropositive nature of ZTF-8 make it a suitable candidate as a polymer-free triboelectric positive material in TENG with outstanding performance (power density of 720 mW/m2). High triboelectric output was further validated using the COMSOL Multiphysics simulation tool. Simple mechanical hand tapping of the ZTF-based TENG (ZTF-TENG) device generates high electric output, which was practically used to power numerous low-powered devices like tally counter, clinical thermometer, and digital clock and also illuminates 125 light-emitting diodes. In addition, the efficiency of ZTF-TENG was utilized as a self-powered device for a selective dopamine (DA) sensor with good sensitivity (377.76 mV/μM/cm2), wide range linearity (5–120 μM), and excellent limit of detection (0.42 μM).