The ionic self-assembly monolayer process is a novel technique that has already been used to deposit ultrathin films on glass, polymer, and silicon substrates of different sizes and shapes. This technique is presented as a new tool with which to apply coatings on optical fibers. A nanometer-scale interferometric cavity was built up at the end of an optical fiber with discrete thickness increments of 4.75 nm for a total thickness of 1 mum . Theoretical and experimental aspects of the nanometer-scale Fabry-Perot cavity are described, and both theoretical and experimental results show good agreement.