This work reports the surface photochemistry study of alloxazine adsorbed within nanochannels of MFI zeolites, namely in a series of Na+ and H+ ZSM-5 zeolites where the hydrophobic and hydrophilic character of the host varies systematically. Laser-induced room temperature and 77 K luminescence of air-equilibrated solid powdered samples of alloxazine adsorbed onto the two sets of zeolites, which we will name NaZSM-5 and HZSM-5, revealed the existence of a single emission of alloxazine as a broad band centred at about 450 nm in some cases, while in others an emission with a maximum at about 510 nm was detected. The decay times of the alloxazine emission vary greatly going from solution to entrapment within the nanochannels of the ZSM-5 zeolites. In the latter case a lifetime distribution analysis has shown that the longest lifetime for the alloxazine. uorescence emission exists in the case where an isoalloxazine-type emission was detected, i.e. whenever the hydrophobic character of the host increases. Alloxazine entrapped in the more acidic zeolites exists in the form of emissive monomers. However, alloxazine emits both from monomeric and aggregated emissive forms in the case of the hydrophobic zeolites. These data indicate the formation of planar dimers of alloxazine whenever the number of active sites in the zeolite decreases. These dimers have to be formed at the intersections of the zig-zag and linear nanochannels of the zeolite since there is no space available for their formation inside the zeolite channels. The isoalloxazine tautomers are formed due to the existence of alloxazine dimers which may undergo double proton transfer in the excited state, following laser excitation. Delayed. uorescence of alloxazine was also detected for the HZSM-5 and NaZSM-5 entrapment both at room temperature and at 77 K. The present study is paradigmatic as regards the host influence on the photochemistry of the guest.