An optical fiber Fabry-Perot (F-P) interferometer end surface was modified using layer-by-layer assembly and chemical covalent cross linking method, and the refractive index (RI) response characteristics of coated optical fiber F-P sensor were experimentally studied. Poly diallyldimethylammonium chloride (PDDA) and sodium polystyrene sulfonate (PSS) were chosen as nano-film materials. With the numbers of layers increasing, the reflection spectral contrast of optical fiber F-P sensor presents from high to low, then to high regularity. And the reflection spectral contrast has good temperature stability. The reflection spectra of the optical F-P sensor coated with 20 bilayers for a series of concentration of sucrose and inorganic solution were measured. Experimental results show that the inflection point extends from 1.457 to 1.462 3, and the reflection spectral contrast sensitivity to low RI material and high RI material is 24.53 and 3.60 dB·RI-1, respectively, with good linearity. The results demonstrate that the functional coated optical F-P sensor provides a new method for biology and chemical material test.