Triboelectric nanogenerators (TENG) are increasingly considered as a promising energy harvesting system due to high output performance from various wasted energy sources. Numerous studies addressing the TENG configuration improve the performance of these devices by optimizing the paired triboelectric materials and structural geometry. Here, poly(1H,1H,2H,2H-perfluorodecyl methacrylate) (PFDMA) fluoropolymer is adopted as a novel negative tribo-material for application to a TENG, as it is at the topmost negative position of the triboelectric series and it is possible to tune the surface roughness under mild conditions. The intrinsic properties are examined and systematic measurements are carried out with the goal of applying the material to a TENG. PFDMA is suitable for application to a TENG, because PFDMA-TENG exhibits a high voltage, current, and power density of 68 V, 6.68 mu A, and 150 mu W, respectively, under a load of 500 MO. Moreover, a PFDMA film offers two distinctive advantages making it ideal for application to a TENG:transmittance higher than 98% even with a relatively high surface roughness, and transfer printing on diverse substrates. The results indicate that PFDMA is a novel negative tribo-material candidate for the fabrication of a TENG with superior triboelectric performance by controlling the surface charge density and morphology.