The photophysical behavior of Coumarin 1 (Coul), a wellknown 7-aminocoumarin derivative, is very sensitive to the microenvironment in which it resides. In the present study, the effect of six bile salt variants on the photophysical behavior of Coul has been investigated. Dihydroxy (deoxycholates) as well as trihydroxy (cholates) bile salts with conjugated and unconjugated side chains have been chosen to get insight into the role of bile salt structure on the microenvironment of Coul. Coul photophysics was found to be extremely sensitive to the aggregation process of the bile salt variants. The reduced polarity of the micellar environment stabilizes the planar intramolecular charge transferred state of Coul, resulting in significant modulation in its photophysics in the bile salt media. The changes in the fluorescence parameters such as fluorescence intensity, emission energy, fluorescence quantum yield, anisotropy, and lifetime of Coul reveal that there is a distinct difference in the aggregation behavior of deoxycholates from that of cholates. The deoxycholates form micelles more or less critically similar to those of conventional surfactants, whereas the cholates self- assemble rather noncritically over a wide concentration range, thus signifying the vital role of the extra hydroxyl group in the aggregation pattern of trihydroxy bile salts. The conjugated bile salts are found to provide a relatively more compact, rigid, and hydrophobic microenvironment to Coul as compared to their unconjugated counterparts. Considering the significant modulation in the photophysical properties of Coul, it has been employed as a molecular reporter for monitoring the aggregation process of bile salt variants and important information could be obtained about the effect of bile salt structure on the aggregation pattern and also about the micellar properties.