The RI-MP2 and RI-CC2 methods have-been,employed to determine the potential energy profiles of neutral and protonated alpha-naphthol, in their individual forms and microhydrated with 1 and 3 water molecules, at different electronic states. According to calculated results, it has been predicted that dynamics of nonradiative processes, in protonated alpha-naphthol is essentially different from that of its neutral homologue:, In protonated alpha-naphthol, the calculations reveal that (1)sigma pi* state, is the most important photophysical state, halting a bound nature with a broad potential curve along the OH coordinate of isolated system) while it is, dissociative in monohydrated homologue. In neutral system, similar to phenol), the (1)sigma pi* state, plays the fundamental relaxation role along the O-H stretching coordinate. Moreover, microhydration strongly affects the photophysical properties Of alpha-naphthol, mostly by alteration of the (1)pi pi* PE profile, from a bound state in an isolated analogue to a dissociative state in hydrated systems. Furthermore, it has been found that three water molecules are necessary for ground state proton transfer between protonated alpha-naphthol and watery with a small barrier; (Delta E< 0.1 eV).