Recently, long-range surface plasmon resonance (LRSPR) sensor has attracted a great deal of attention as a potentially non-destructive and label-free technique for cellular studies in real time. Thus, much effort has been placed on the fabrication and optimization of multilayered structure required for the excitation of LRSPR. In this work, a detailed study about the influence of both plasma polymerized dielectric buffer layer (DBL) and thin gold film on the excitation of LRSPR was performed. The DBLs of different thicknesses were deposited directly onto SF11 glass slides by radio frequency plasma polymerization (pp) of perfluorooctyl ethylene (PFOE). Thereafter, Au films of different thicknesses were thermally evaporated onto the ppPFOE layers. Atomic force microscopy (AFM) results suggest that the resulting SF11/ppPFOE/Au structure has a smooth surface regardless of Au film’s thickness. LRSPR measurements indicate that the excitation of LRSPR relies not only on the thickness of the ppPFOE buffer layer, but also on the thickness and optical property of thin Au film. Theoretical simulation based on Fresnel’s equation allows for the determination of both the thickness and optical constant of each layer supporting the LRSPR, and also enables us to predict the optimum combination of ppPFOE and Au film in a LRSPR sensor. The performance of various LRSPR sensors to monitor the bulk refractive index variation has also been investigated.