A triboelectric nanogenerator (TENG) with an ultra-thin thickness of a tribo-dielectric layer (TDL) composed of poly heptadecafluorodecyl methacrylate (PFDMA) is demonstrated. The thickness of the PFDMA, which serves as the TDL, was precisely controlled within a range of 0.5 mu m-12 mu m through the use of initiated-chemical vapor deposition (i-CVD). The relationship between the TDL thickness and the output characteristics was analyzed by demonstrating the ultra-thin TDL thickness, which is the thinnest thickness polymer TDL ever reported. As the TDL thickness is increased, the short-circuit current (I-SC) and the transferred charge (Q(TR)) both increase while the open-circuit voltage (V-OC) remains constant. Because a TENG with the ultra-thin TDL shows a different tendency between Q(TR) and the total charge (Q(TDL)) in the TDL, modeling is also carried out to gain a comprehensive understanding of the TDL thickness and output characteristics.