The steady-state fluorescence and dilatometric techniques were used to study the free-radical crosslinking copolymerization of styrene (S) and commercial divinylbenzene (DVB) in bulk. Pyrene (Py) was used as a fluorescence probe for the in situ polymerization experiments. The time required for a sudden increase in the fluorescence intensity of Py was recorded for various DVB content and temperature. The monomer conversions and the gel points were recorded by dilatometry. To interpret the experimental data, a kinetic model was developed for the S-DVB copolymerization system. It was shown that both the pendant vinyl groups and Py molecules are affected by the reaction medium in a similar way, their mobility decreases as the DVB concentration increases or the temperature decreases. The reaction time at which the Py intensity in the fluorescence spectra exhibits a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. The results show that the fluorescence technique can be used to follow the onset of the gel effect in S-DVB copolymerization.