A new asymmetric perfluordiarylethene (1O) was synthesized using 4, 5-[bis-(5-ethylacetate-yl)-2-thienyl]-1H-imidazole as a functional group. 1O exhibited favorable reversible cyclization and cycloreversion reactions upon alternating irradiation with UV and visible light. Both of its open- and closed-ring isomers were found to be highly selective towards Cu2+ with significant absorption and color changes, which could be used as a ‘naked-eye’ colorimetric sensor for Cu2+ detection. Upon exposure to acid, its fluorescence dramatically enhanced by 14-fold with a color change from dark to bright cyan due to the formation of the protonated compound. Moreover, 1O showed obvious fluorescence “turn-on” signal response towards Al3+, and the detection limit for Al3+ was determined to be 4.8 × 10−9 mol L−1. Based on the fluorescence signals of 1O, a combinational stimuli logic circuit were designed by using the fluorescence intensity as the output signal with the inputs of lights, Al3+ and EDTA. Finally, 1O could be used as a biological probe for detecting intracellular Al3+ in a physiological environmental.