The transient absorption spectrum of 1-naphthol was first sought by flash photolysis at higher acidities than had been previously investigated. While no transient absorption was observed for l-naphthol itself, strong transient absorptions were observed for l-naphthol-2 and -4-sulphonates even in aqueous solution. This enabled pK(T1) for the protonation of the naphtholate ions to be measured directly from the strength of triplet-triplet absorptions and this value was compared with the pK(T1) obtained from Forster Cycle calculations on phosphorescence maxima,. Values of pK(S1) and pK(S0) were also obtained and the order of the pK values was found to be pK(S0) > pK(T1) >> pK(S1), It is likely that this order is the same for l-naphthol and therefore disagrees with the results of some recent quantum mechanical calculations, A strong fluorescence was also observed for l-naphthol-2- sulphonate in aqueous acidic solutions, in contrast with the weak fluorescence observed for 1-naphthol and l-naphthol-4-sulphonate. This is explained in terms of intramolecular hydrogen bonding in l-naphthol-2-sulphonate which prevents quenching of the first excited singlet state by hydrogen bonding with solvent water molecules. The fluorescence intensity of 1-naphthol, l-naphthol-2-sulphonate, and l~naphthol-4-sulphonate in aqueous acidic solutions is also found to increase as the water concentration is effectively reduced by the addition of certain solutes in large quantities, A corresponding increase in the triplet yield is also found for l-naphthol-2-sulphonate in acidic solutions. These increases are also explained in terms of reducing the hydrogen bonding to solvent water molecules and hence reducing the deactivation of the state, l-Naphthol sulphonates and protonates in concentrated sulphuric acid and it is deduced that protonation occurs at a carbon atom in the naphthalene ring, A value of pK(S0 ) was determined for this protonation.