A novel class of fluorescent immuno-biolabeling systems with extremely high F/P ratio (approximately 1000-6000) were prepared by combining the template method and layer-by-layer (LbL) technique. Labels were constructed by loading organic dye fluorescein diacetate (FDA) molecules onto hollow periodic mesoporous organosilica (H-PMO) particles followed by ployelectrolyte encapsulation and antibody attachment. The labeling systems were stimuli-responsive to the addition of concentrated NaOH with the loaded dye molecules being released and detected in a well-controlled manner. When applied in sandwich immunoassays, results indicated that the biolabels were immuno-active and generated an optimal signal that was approximately 50 times higher than the conventional dye labelled antibody system.