Due to their reversible diol-binding ability, phenylboronic acid (BA) derivatives have gained considerable interest for the development of saccharide sensors and drug delivery systems. In particular, BA-containing polymers have been used for the realisation of sugar-responsive layerby-layer (LbL) films. Herein, a LbL system based on cationic BA-homopolymers (PBA) is presented, and its subsequent sugar-induced disassembly is described. The BA-linear polymers (PBA) were intercalated with poly(vinylsulfonic acid, sodium salt) to form (PBA/PVS)n film assemblies. Different orientations of the boronic acid substituent (ortho-, meta-and para-) in the PBA polymer were investigated for their influence on the LbL assembly. The rate of disassembly in the presence of glucose or fructose was analyzed by UV-vis spectroscopy. Additionally, the PVS component was replaced by an anionic fluorophore, pyranine (PYR), which allowed the assembly and disassembly to be monitored by fluorescence.