Developing highly sensitive fluorescent probe for Al3+ and H2O detection is highly desirable, due to aluminum toxicity poses a significant threat to public health. On the other hand, the determination of water content holds immense significance in a wide range of fields such as food processing, pharmaceutical manufacturing. In this paper, a novel acylhydrazone-based fluorescent probe P was successfully synthesized and characterized for the sequential detection of Al3+ and water in alcohols. The probe P exhibited a remarkable “turn-on” response towards Al3+ by emitting yellow fluorescence at 567 nm, with high selectivity and large Stokes shift (147 nm). Meanwhile, the in situ formed P-Al3+ complex demonstrated significant solvatofluorochromic characteristic, which could be utilized as a second probe for detecting water via fluorescence quenching with low detection limit in alcohols (0.008%, methanol; 0.013%, ethanol; 0.013%, isopropanol; 0.037%, n-butanol; vol.%) and acetonitrile (0.072%, vol.%). Moreover, the P-Al3+ complex was able to detect the alcoholic strength of Chinese Baijiu without the interference of other alcohols, providing an excellent recovery rate (100.0–107.0%). Different Chinese Baijius, with various alcoholic strength, could be distinguished by simple test strips. Furthermore, the P-Al3+ complex could also analyze the water content in organic solvents.