A novel "turn-on" fluorescent bioprobe, 1,2,3,4,5-penta(4-carboxyphenyl)pyrrole sodium salt (PPPNa), with aggregation-enhanced emission characteristics was synthesized for the in situ quantitative detection of Al in serum. It exhibited a high selectivity to Al in both simulated serum and fetal calf serum with no interferences from other metal ions or serum components observed and no isolation required. A weak interaction between PPPNa and serum albumin was found, which caused no interference, but enhanced fluorescence response of PPPNa to Al and improved detection sensitivity. The limit of detection was determined to be 1.50 μmol/L Al in phosphate-buffered saline solution containing 33 μg/mL bovine serum albumin (BSA) and decreased to 0.98 μmol/L as BSA concentration increased to 100 μg/mL. The fluorescence "turn-on" mechanism of the PPPNa probe to detect Al was proposed. A bidentate complex is formed between the carboxy group of PPPNa and Al, causing the photoluminescence (PL) emission enhancement by aggregation. BSA chains further strengthen the stacking compactness of the aggregates of PPPNa and Al and consequently enhance the PL emission of PPPNa by further promoting the restriction of intramolecular rotation of the phenyl ring. Its application to the in situ Al was successfully demonstrated with HeLa cells and NIH 3T3 cells. The low cytotoxicity and highly selective response of PPPNa to Al endow its great potentials to in vivo detecting and imaging of Al as well as an absorbent of Al.