We developed a simple dual signal (color and 'Off-On' fluorescent change) ensemble system based on the complex between a rhodamine derivative 1 and Al(3+) for the detection of pyrophosphate (PPi) in 100% aqueous solutions. The complex between the rhodamine compound and Al(3+) was utilized as a chemosensing ensemble for the first time. The ensemble showed highly sensitive and selective fluorescent and colorimetric response to pyrophosphate among the anions in 100% aqueous solutions and no interference of the potent biological competitors including ATP, ADP, and phosphate for the detection of PPi in 100% aqueous solutions at pH 7.4.