Functional nanocoatings have allowed hollow-core microstructured optical fibers (HC-MOFs) to be introduced into biosensing and photochemistry applications. However, common film characterization tools cannot evaluate the coating performance in situ. Here we report the all-optical noncontact characterization of the HC-MOF coating in real time. Self-assembled multilayers consisting of inversely charged polyelectrolytes (PEs) are deposited on the HC-MOF core capillary, and a linear spectral shift in the position of the fiber transmission minima with increasing the film thickness is observed as small as ∼1.5 − 6 nm per single PE bilayer. We exemplify the practical performance of our approach by registering an increase in the coating thickness from 6 ± 1 to 11 ± 1 nm per PE bilayer with increasing ionic strength in the PE solutions from 0.15 to 0.5 M NaCl. Additionally, we show real-time monitoring of pH-induced coating dissolving. Simplicity and high sensitivity make our approach a promising tool allowing noncontact analysis of the HC-MOF coating which is still challenging for other methods.