We prepared an azo dye rotaxane and its polymeric metal complex and successfully demonstrated their useful application for dyeing silica fiber, which exhibited high-color strength and fairly good color fastness. These benefits were made possible by the hydrogen bonding between SiO2 and hydroxyl groups (?OHs) on a-cyclodextrin (a-CD). Spectroscopic evidence supports the formation of polymeric metal-complexed rotaxanes within the silica fiber. The current results are meaningful because they indicate that the proper adjustment of the interaction between CD and SiO2 can produce CD-encapsulated dyes that provide an effective platform for depositing various metal ions on silica surfaces, which will be useful in numerous promising applications. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013