Semi-empirical (AM1±SCI) calculations have been performed on 2-(2 0 -hydroxyphenyl)oxazole (HPO), 2-(2 0 -hydroxyphenyl)imidazole (HPI) and 2-(2 0 -hydroxyphenyl)thiazole (HPT) to rationalise the photophysical behaviour of the compounds exhibiting intramolecular rotation as well as excited state intramolecular proton transfer (ESIPT). The calculations reveal that there is a gradual variation in the properties from HPO to HPT through HPI so far as the existence of the rotational isomers in the ground state is concerned. While HPO gives rise to two stable rotamers (I and II) in all the common solvents, there is only one stable species for HPT in the S 0 state. For HPI, rotamer II is possible only in the isolated state and/or in solvents of low polarity, but in high polar solvents it gives rise to the normal form (I) only. For all the molecules in the series, however, intramolecular proton transfer (IPT) takes place in the lowest excited singlet (S 1 ) and the triplet (T 1 ) states. Combination of the rotamerism and ESIPT gives rise to multiple¯uorescence bands for the¯uorophores. Theoretical assignments have been made for the excitation,¯uorescence and phosphorescence bands. Simulated potential energy curves (PEC) in different electronic states reveal that the IPT process is feasible in either of the S 1 and T 1 states but not in the ground state. The ESIPT reaction has been found to be favoured both thermodynamically and kinetically in these electronic states compared to the ground state. However, quantum mechanical tunnelling has been proposed for the prototropic reaction to proceed in the excited states. q