Polyelectrolyte multilayer microcapsules were prepared by a layer-by-layer deposition of poly(ethyleneimine) (PEI) or poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) on a calcium carbonate particle containing fluorescein isothiocyanate-concanavalin A (FITC-Con A)/glycogen conjugates. Fluorescence microscope and scanning electron microscope observations revealed that the microcapsules thus prepared are spherical with a diameter of 3–5 μm. The fluorescence intensity of the microcapsules was enhanced upon addition of sugars, depending on the type of sugar and its concentration. The enhanced fluorescence intensity was rationalized by sugar-induced decomposition of the FITC-Con A/glycogen conjugates and resulting dequenching of the fluorescence of FITC-Con A. The capsule can be used repeatedly a few times after washing in buffer solution, although FITC-Con A leaked out of the capsules gradually.