In this paper, we report on the tunable metal‐enhanced fluorescence (MEF) of Ag nanostructures. Because of the good MEF properties of the highly dendritic Ag nanostructures, we obtained an increase of up to 25 times for the weak fluorescence of porphyrin molecules (Por4–). More importantly, by the introduction of a stimulus‐responsive PAA/PDDA multilayer film as an interlayer, the distance between the fluorophores and the Ag nanostructures could be tuned by immersing the substrates into solutions of different ionic strength or pH. The MEF behavior of the composite films could thus be tuned in a controlled manner, because of the distance dependent nature of the MEF effects.
