Fluorescence spectroscopy has been widely used to monitor different polymer processes such as polymerization kinetics, chain entanglements, and thermal transitions. The solvent-free controlled ring-opening polymerization (ROP) of lactide is significant both commercially and for research; thus, monitoring this process with a simple fluorescence method can be very useful. Here, a fluorescent dye, difluoroboron 4-methoxydibenzoylmethane (BF(2)dbmOMe) is employed to probe lactide bulk ROP by measuring the emission from solidified reaction aliquots at room temperature. It was found that, through the course of polymerization, the fluorescence of BF(2)dbmOMe in the solid-state aliquots exhibited a systematic shift from yellow to green and then to blue, accompanied by a gradual reduction in the decay lifetime. The fluorescence color change is sensitive to the monomer percent conversion, not the polymer molecular weight. On the basis of these observations and experimental data, we propose that the long-wavelength emission with perceivably longer lifetimes arises from BF(2)dbmOMe dye aggregates (ground and/or excited states), while the dissolved individual dye molecules are responsible for the blue fluorescence with a shorter lifetime. This demonstration of the utility of BF(2)dbmOMe as a fluorescent probe for lactide polymerization could have important practical implications.