This article reports an efficient host-assisted guest protonation mechanism in coumarin 6 (C6) dye, upon its interaction with cucurbit[7]uril (CB7) macrocycle. C6 uptakes the CB7 macrocycle both in 1:1 and 2:1 (CB7/C6) stoichiometries, which brings out a large upward pK(a) shift (from similar to 0.8 to 6), and facilitates the protonation of C6 at normal pH conditions, having significant photochemical implications. Controlled dissociation of the assemblies has been achieved through their response to stimuli like temperature change or metal ions. By this approach, a specific form of the guest can be activated and could provide a simple stimulus for the controlled drug/dye delivery. Furthermore, the host-assisted guest protonation improves the stability and aqueous solubility of C6 and is a promising candidate for aqueous-based supramolecular dye laser system. Such simple protocol leading to photoswitchable systems having aqueous solubility and biocompatibility can in principle be evolved into a general strategy to deliver and operate potential functional molecular components under various trigger control.