Novel microcapsule systems containing UV-responsive diazonium groups were fabricated as microcontainers for cargo substance encapsulation by using a layer-by-layer (LbL) assembly technique. Upon direct exposure to UV light with a wavelength of approximately 380 nm, the diazonium groups of diazoresion (DAR) rapidly reacted with sulfonate or diazo-sulfonate groups of counterpart polyelectrolytes, which converted electrostatic interactions to covalent bonds, demonstrating an effective in situ cross-linking within multilayers via photolysis. Such chemical transition eliminated the paired ionic groups, therefore generating more hydrophobic multilayer shells, offering a unique approach to seal the porous polyelectrolyte capsule shells. Fluorescent molecule rhodamine B (RhB) was consequently studied as a typical example for small molecule encapsulation. Results indicated that the dye was remarkably retained within the microcapsules after UV-triggered capsule shell sealing.