Gelatin reactivity with isocyanate was studied by using the easy detectable 1-naphthyl-isocyanate (NphI). Four different NphI/gelatin feed ratios were investigated with NphI molar amount ranging between 1/10 and 1/1 with respect to the possible reactive groups of gelatin. The reactions were carried out at 45 A degrees C in DMSO as solvent, under nitrogen atmosphere. Modified gelatin samples were characterized by IR, UV-VIS, fluorescence spectroscopies as well as by proton and DOSY NMR. Spectroscopy results allow to evidence the presence of both bonded and unbonded naphthyl derivatives in the gelatin samples. Unbonded species were present particularly at the highest NphI/gelatin feed ratio and their formation was correlated to the increasing competition of the reaction with water since the amount of available reactive groups on gelatin was comparable or smaller than the amount of residuum water in dry gelatin.