A novel approach to chemical application of long period grating (LPG) optical fibers was demonstrated, which were modified with a film nanoassembled by the alternate deposition of SiO(2) nanoparticles (SiO(2) NPs) and poly(diallyldimethyl ammonium chloride) (PDDA). Nanopores of the sensor film could be used for sensitive adsorption of chemical species in water, which induced the changes in the refractive index (RI) of the light propagating in the cladding mode of the optical fiber, with a concomitant effect on the transmission spectrum in the LPG region. The prepared fiber sensor was highly sensitive to the change in the RI of the surrounding medium and the response time was very fast within 10 s. In addition, chemical infusion into the film was tested using a porphyrin compound, tetrakis-(4-sulfophenyl)porphine (TSPP), which could be saturated within a few min. The lowest detectable concentration of the TSPP analyte was 10 microM. The TSPP infusion led to the development of well-pronounced dual resonance bands, indicating a large increase in the optical thickness of the film. The RI of the film was dramatically increased from 1.200 to ca. 1.540.