A novel technique based on steady-state fluorescence measurements was introduced to study free-radical polymerization of 2-vinylnaphthalene (2VN). Both spectroscopic and kinetic studies of polymerization of 2VN in toluene solution have been carried out over the temperature range between 50 and 70 degreesC. The effective radius of interaction of 2VN required for excimer formation was found to be around 3.5 nm. The product of reaction rate constant k(p) and steady-state radical concentration [M .], k(p)[M .] was calculated for 2-vinylnaphthalene (2VN) polymerization carried out at the temperatures 50, 60, 65, and 70 degreesC. A sudden change in the value of k(p)[M .] was observed above 60 degreesC, indicating that polymerization proceeds effectively just at and above this temperature.