This work reports on the naphthalene based chemosensor for selective detection of Al3+ in aqueous solution based on photoinduced electron transfer (PET) process. Fluorescent sensors with naphthalene unit have been prepared and characterized. Their complexation behavior and binding mode towards Al3+ and other metal ions have been studied by UV-vis, fluorescence spectrometric and Mass Spectrometry method. Receptor 1-(1H-benzo[d]imidazol-2-yl) naphthalene-2-ol, exhibits highly selective and sensitive recognition of Al3+ over other heavy and transition metal ions. The “off-on” fluorescent recognition of Al3+ by 1-(1H-benzo[d]imidazol-2-yl) naphthalene-2-ol is free from the interference of other metal ions. Therefore, the sensor 1-(1H-benzo[d]imidazol-2-yl) naphthalene-2-ol could be used as a potential probe to detect aluminum ions in the biological and environmental monitoring works.