The Electrostatic Self-Assembly (ESA) technique possesses great advantages over traditional thin film fabrication methods, making it an excellent choice for a number of applications in the fields of linear and nonlinear optics, electronics, sensing and surface coatings. The feasibility of fabricating linear optical interference filters by ESA methods is demonstrated in this thesis work. Basic single-anion/single-cation ESA films are synthesized and their optical parameters -- refractive index and average thickness for individual bilayer -- are investigated to provide a basis for the in-depth design of optical filters. High performance dielectric stack filters and narrowband and wideband antireflection coatings are designed using TFCalc simulation software and are fabricated by ESA. Both bulk film sensitivity and layer sensitivity to manufacturing errors are provided. The significant agreement between simulation and experiment demonstrates the strong capability of ESA to precisely control the refractive index and produce excellent thin film filters. The performance of optical thin film filters is largely enhanced compared to the results of previous methods. The experiment results indicate that the ESA process may be used to fabricate optical filters and other optical structures that require precise index profile control.