The absorption of dyes within hydrogen-bonded and electrostatically assembled multilayers and subsequent release of the dyes from the films were studied in situ using FTIR-ATR. Multilayers were composed of poly(methacrylic acid), PMAA, and poly(ethylene oxide), PEO (hydrogen-bonded multilayers), or of PMAA and 22% quarternized copolymer of N-ethyl-4-vinylpyridium bromide and 4-vinylpyridine, Q22 (electrostatically stabilized multilayers). After multilayer deposition, the solution pH was changed to produce excess charge within the films. Dyes with charge opposite to the excess charge of the film (Rhodamine 6G for hydrogen-bonded films or Bromophenol Blue for electrostatically assembled multilayers) were then allowed to absorb within multilayers. In both systems, the dyes were uniformly included within the films. The top layers largely affected the loading capacity of the multilayers, suggesting weaker binding of the dyes with the top layers. Dye release into a 0.01 M phosphate buffer was significantly smaller as compared to release in the presence of 0.05-0.5 mg/mL solutions of adsorbing polymers whose charge was the same as the excess charge within the films. We found that with the PMAA/PEO films, dye release did not depend on the concentration of polymer in solution, but was largely controlled by the amount of charge accumulated within the adsorbing polymer layer on the top of the film. For electrostatically stabilized PMAA/Q22 systems, dye release increased with increasing concentration of Q22 in solution, suggesting a significant contribution of the competition of solution species in the release mechanism. Our findings contribute to the understanding of interactions of small molecules with polymer multilayers and might have ramifications for novel applications of multilayer films as new materials for the controlled delivery of chemicals.